Catalyst compounds and use thereof

ABSTRACT

This invention relates to Group 4 dialkyl compounds supported by a pyridyl-amido-aryl (“PAA”), an anisole-amido-aryl (“AAA”), a phenoxy-amido-pyridyl (“PAPY”), an anisole-amido-phenoxy (“AAP”) or a anisole-amido-phenoxy (“AAP”) tridentate ligand. Such compounds can polymerize olefins, such as ethylene.

PRIORITY CLAIM

This application claims priority to and the benefit of U.S. Ser. No.61/255,758, filed Oct. 28, 2009 and EP 09178617.8, filed Dec. 10, 2009.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is related to U.S. Ser. No. 61/255,742, filed Oct. 28,2009; U.S. Ser. No, 61/255,725, filed Oct. 28, 2009; U.S. Ser. No.61/255,706, filed Oct. 28, 2009; and U.S. Ser. No. 61/255,750, filedOct. 28, 2009. This application is also related to:

1) U.S. Ser. No. 12/908,522, filed Oct. 20, 2010 claiming priority toU.S. .Ser. No, 61/255,750, filed Oct. 28, 2009;

2) U.S. Ser. No. 12/908,257, filed Oct. 20, 2010 claiming priority toU.S. Ser. No. 61/255,742, filed Oct. 28, 2009;

3) U.S. Ser. No. 12/908,268, filed Oct. 20, 2010 claiming priority toU.S. Ser. No. 61/255,725, filed Oct. 28, 2009; and

4) U.S. Ser. No. 12/908,550, filed Oct. 20, 2010 claiming priority toU.S. Ser. No. 61/255,706, filed Oct. 28, 2009.

FIELD OF THE INVENTION

This invention relates to catalyst compounds useful for polymerizationand or oligomerization of unsaturated monomers, such as olefins.

BACKGROUND OF THE INVENTION

Various processes and catalysts exist for the homopolymerization orcopolymerization of olefins. New polymerization catalysts are ofinterest in the industry because they offer many new opportunities forproviding new processes and products to the markets in a cheaper andmore efficient manner.

References of general interest related to the instant invention include:WO 2000/020427, WO 2001/010875, WO 2003/054038, U.S. Patent Publication20080182952, Polymer International, (2002) 51 (12), 1301-1303,Collection of Czechoslovak Chemical Communications (1988), 63(3),371-377, and Transition Metal Chemistry (London) (1988) 23 (5), 609-613.

There is a need, therefore, for new polymerization technology, catalystsand products produced therefrom that are based on new transition metalcatalyst compounds.

SUMMARY OF THE INVENTION

Group 4 catalyst compounds containing di-anionic tridentatenitrogen/oxygen based ligands are provided. The catalyst compounds areuseful, with or without activators, to polymerize olefins, particularlyα-olefins, or other unsaturated monomers. Systems and processes tooligomerize and/or polymerize one or more unsaturated monomers using thecatalyst compound, as well as the oligomers and/or polymers producedtherefrom are also provided. For the purposes of this disclosure,“α-olefins” includes ethylene.

The catalyst compounds can be represented by the following structures:

wherein

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 0, 1, 2 or 3;

each R¹ and R² if resent R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³ andR¹² if present, is independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl,preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is a group 4 metal, preferably Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L; and

n is 1 or 2.

In one particular embodiment, n is 1 and w is 2 or 3.

In another embodiment, it is possible that where R¹² is a hydrogen atomin the ligand (for A and B), the carbon bonded to R¹² may or may notreact with M such that an anionic ligand X is eliminated in the form ofHX to form a bond between the carbon atom at the R¹² site and M suchthat w=2, 1 or 0 which is dependent on “n”.

In still another embodiment, the present invention provides catalystcompositions which include one or more of the above-described catalystcompounds and one or more activators.

Definitions

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, and an arrow indicates that the bond maybe dative.

As used herein, the new notation for the Periodic Table Groups is usedas described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

Neutral ligands are defined as ligands that are neutral, with respect tocharge, when formally removed from the metal in their closed shellelectronic state. Neutral ligands contain at least one lone pair ofelectrons, pi-bond or sigma bond that are capable of binding to thetransition metal. Neutral ligands may also be polydentate when more thanone neutral ligand is connected via a bond or a hydrocarbyl, substitutedhydrocarbyl or a functional group tether. A neutral ligand may be asubstituent of another metal complex, either the same or different, suchthat multiple complexes are bound together.

Anionic ligands are defined as ligands that are anionic, with respect tocharge, when formally removed from the metal in their closed shellelectronic state. Anionic ligands include hydride, halide, hydrocarbyl,substituted hydrocarbyl or functional group. Non-limiting examples ofanionic ligands include hydride, fluoride, chloride, bromide, iodide,alkyl, aryl, alkenyl, alkynyl, allyl, benzyl, acyl, trimethylsilyl.Anionic ligands may also be polydentate when more than one anionicligand is connected via a bond or a hydrocarbyl, substituted hydrocarbylor a functional group tether. An anionic ligand may be a substituent ofanother metal complex, either the same or different, such that multiplecomplexes are bound together. A mono-anionic ligand is defined to be ananionic ligand that has a −1 charge. A di-anionic ligand is defined tobe an anionic ligand that has a −2 charge.

The terms “hydrocarbyl radical,” “hydrocarbyl” and hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group” and “substituent” are also used interchangeably in thisdocument. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁-C₁₀₀ radicals, that may be linear, branched, or cyclic(aromatic or non-aromatic); and include substituted hydrocarbylradicals, halocarbyl radicals, and substituted halocarbyl radicals,silylcarbyl radicals, and germylcarbyl radicals as these terms aredefined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR^(*), PR^(*) ₂, AsR*₂, SbR*₂, SR*, BR*₂,SiR*₃, GeR*₃, SnR*₃, PbR*₃ and the like or where at least onenon-hydrocarbon atom or group has been inserted within the hydrocarbylradical, such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂,SnR*₂, PbR*₂ and the like, where R* is independently a hydrocarbyl orhalocarbyl radical.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g. F,Cl, Br, I) or halogen-containing group (e.g. CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃ and the like or where at least onenon-carbon atom or group has been inserted within the halocarbyl radicalsuch as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*₂, GeR*₂, SnR*₂,PbR*₂ and the like where R* is independently a hydrocarbyl or halocarbylradical provided that at least one halogen atom remains on the originalhalocarbyl radical.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR^(*) ₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like where R* isindependently a hydrocarbyl or halocarbyl radical as defined above andtwo or more R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH₃, GeH₂R*, GeHR*₂, GeR⁵ ₃, GeH₂(OR*),GeH(OR*)₂, Ge(OR*)₃, GeH₂(NR*₂), GeH(NR*₂)₂, Ge(NR*₂)₃, and the likewhere R* is independently a hydrocarbyl or halocarbyl radical as definedabove and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Polar radicals or polar groups are groups in which the heteroatomfunctionality is bonded directly to the indicated atom or atoms. Theyinclude heteroatoms of groups 1-17 of the periodic table either alone orconnected to other elements by covalent or other interactions such asionic, van der Waals forces, or hydrogen bonding. Examples of functionalgroups include carboxylic acid, acid halide, carboxylic ester,carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen(Group 14) analogues, alcohol and phenol, ether, peroxide andhydroperoxide, carboxylic amide, hydrazide and imide, amidine and othernitrogen analogues of amides, nitrile, amine and imine, azo, nitro,other nitrogen compounds, sulfur acids, selenium acids, thiols,sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphoruscompounds, silanes, boranes, borates, alanes, aluminates. Functionalgroups may also be taken broadly to include organic polymer supports orinorganic support material such as alumina, and silica. Preferredexamples of polar groups include NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂,SbR*₂, SR*, BR*₂, SnR*₃, PbR*₃ and the like where R* is independently ahydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl radical as defined above and two R* may join together to forma substituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl. Also includedare isomers of saturated, partially unsaturated and aromatic cyclicstructures wherein the radical may additionally be subjected to thetypes of substitutions described above. Examples include phenyl,methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, and the like. For this disclosure, when a radical islisted, it indicates that radical type and all other radicals formedwhen that radical type is subjected to the substitutions defined above.Alkyl, alkenyl and alkynyl radicals listed include all isomers includingwhere appropriate cyclic isomers, for example, butyl includes n-butyl,2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

In the context of this document, “homopolymerization” would produce apolymer made from one monomer. For example, homopolymerization ofpropylene would produce homopolypropylene. Homopolymerization ofethylene would produce homopolyethylene. It should be noted, however,that some of the catalysts of this invention homopolymerize ethylene orpropylene to non-traditional “polyethylene” and “polypropylene”structures, respectively. Likewise, “copolymerization” would producepolymers with more than one monomer type. For example, ethylenecopolymers include polymers of ethylene with α-olefins, cyclic olefinsand diolefins, vinylaromatic olefins, α-olefinic diolefins, substitutedα-olefins, and/or acetylenically unsaturated monomers. Non-limitingexamples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene,1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene,1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene,3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene,vinylcyclohexane, and vinylnorbornane. Non-limiting examples of cyclicolefins and diolefins include cyclobutene, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene,4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene,vinylcyclohexane, norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene, vinylcyclohexene, 5-vinyl-2-norbornene,1,3-divinylcyclopentane, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane,1,4-divinylcyclohexane, 1,5-divinylcyclooctane,1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane,1-allyl-5-vinylcyclooctane, and 1,5-diallylcyclooctane. Non-limitingexamples of vinylaromatic olefins include styrene, para-methylstyrene,para-t-butylstyrene, vinylnaphthylene, vinyltoluene, and divinylbenzene.Non-limiting examples of α-olefinic dienes include 1,4-hexadiene,1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene,1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, 1,11-dodecene,1,13-tetradecene and 9-methyl-1,9-decadiene. Substituted α-olefins (alsocalled functional group containing α-olefins) include those containingat least one non-carbon Group 13 to 17 atom bound to a carbon atom ofthe substituted α-olefin where such substitution if silicon may beadjacent to the double bond or terminal to the double bond, or anywherein between, and where inclusion of non-carbon and -silicon atoms such asfor example B, O, S, Se, Te, N, P, Ge, Sn, Pb, As, F, Cl, Br, or I, arecontemplated, where such non-carbon or -silicon moieties aresufficiently far removed from the double bond so as not to interferewith the coordination polymerization reaction with the catalyst and soto retain the generally hydrocarbyl characteristic. By beingsufficiently far removed from the double bond we intend that the numberof carbon atoms, or the number of carbon and silicon atoms, separatingthe double bond and the non-carbon or -silicon moiety may be 6 orgreater, e.g. 7, or 8, or 9, or 10, or 11, or 12, or 13, or 14 or more.The number of such carbon atoms, or carbon and silicon atoms, is countedfrom immediately adjacent to the double bond to immediately adjacent tothe non-carbon or -silicon moiety. Examples includeallyltrimethylsilane, divinylsilane, 8,8,8-trifluoro-1-octene,8-methoxyoct-1-ene, 8-methylsulfanyloct-1-ene, 8-dimethylaminooct-1-ene,or combinations thereof. The use of functional group-containingα-olefins where the functional group is closer to the double bond isalso within the scope of embodiments of the invention when such olefinsmay be incorporated in the same manner as are their α-olefin analogs.See, “Metallocene Catalysts and Borane Reagents in The Block/GraftReactions of Polyolefins”, T. C. Chung, et al, Polym. Mater. Sci. Eng.,v. 73, p. 463 (1995), and the masked α-olefin monomers of U.S. Pat. No.5,153,282. Such monomers permit the preparation of both functional-groupcontaining copolymers capable of subsequent derivatization, and offunctional macromers which may be used as graft and block type polymericsegments. All documents cited herein are incorporated by reference forpurposes of all jurisdictions where such practice is allowed.Copolymerization can also incorporate α-olefinic macromonomers of up to2000 mer units.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-75 mer units and the term polymer refers tocompositions having 76 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the monomer(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene.

The terms “catalyst” and “catalyst compound” are defined to mean acompound capable of initiating catalysis. A catalyst compound may beused by itself to initiate catalysis or may be used in combination withan activator to initiate catalysis. When the catalyst compound iscombined with an activator to initiate catalysis, the catalyst compoundis often referred to as a pre-catalyst or catalyst precursor. The term“catalyst system” is defined to mean: 1) a catalyst precursor/activatorpair, and or 2) a catalyst compound capable of initiating catalysiswithout an activator. When “catalyst system” is used to describe such apair before activation, it means the unactivated catalyst (pre-catalyst)together with an activator and, optionally, a co-activator. When it isused to describe such a pair after activation, it means the activatedcatalyst and the activator or other charge-balancing moiety.

The catalyst compound may be neutral as in a pre-catalyst or a catalystsystem not requiring an activator, or may be a charged species with acounter ion as in an activated catalyst system.

The terms “activator” and “cocatalyst” are used interchangeably herein.A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Insome embodiments a co-activator can be pre-mixed with the catalystcompound to form an alkylated catalyst compound, also referred to as analkylated invention compound.

Noncoordinating anion (NCA) is defined to mean an anion either that doesnot coordinate to the catalyst metal cation or that does coordinate tothe metal cation, but only weakly. An NCA coordinates weakly enough thata neutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center. Any metalor metalloid that can form a compatible, weakly coordinating complex maybe used or contained in the noncoordinating anion. Suitable metalsinclude, but are not limited to, aluminum, gold, and platinum. Suitablemetalloids include, but are not limited to, boron, aluminum, phosphorus,and silicon.

A stoichiometric activator can be either neutral or ionic. The termsionic activator, and stoichiometric ionic activator can be usedinterchangeably. Likewise, the terms neutral stoichiometric activator,and Lewis acid activator can be used interchangeably.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to Group 4 dialkyl compounds supported by apyridyl-amido-aryl (“PAA”), an anisole-amido-aryl (“AAA”), aphenoxy-amido-pyridyl (“PAPY”), an anisole-amido-phenoxy (“AAP”) or aanisole-amido-phenoxy (“AAP”) tridentate ligand. Such compounds canpolymerize ethylene to produce polyethylene. The catalyst compounds canbe represented by the following structures:

wherein

each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl;

w is 0, 1, 2 or 3;

each R¹ and R² if resent R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³ andR¹² if present, is independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl,preferably, a C₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substitutedhydrocarbyl, a C₁ to C₃₀ halocarbyl, or a C₁ to C₃₀ substitutedhalocarbyl, more preferably a C₁ to C₁₀ hydrocarbyl, a C₁ to C₁₀substituted hydrocarbyl, a C₁ to C₁₀ halocarbyl, or a C₁ to C₁₀substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, aphosphide, a silyl or another anionic heteroatom-containing group; orindependently, may join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure;

L is a neutral ligand bonded to M that may include molecules such as butnot limited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like;

M is a group 4 metal, preferably Hf, Zr or Ti;

m is 0, 1 or 2 and indicates the absence or presence of L; and

n is 1 or 2.

In one particular embodiment, X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², R¹³, L, M, and m are as defined above and n is 1 and w is2 or 3. Such catalyst compounds can be represented by the structures:

In another embodiment, it is possible that where R¹² is a hydrogen atomin the ligand (for A and B), the carbon bonded to R¹² may or may notreact with M such that an anionic ligand X is eliminated in the form ofHX to form a bond between the carbon atom at the R¹² site and M suchthat w=2, 1 or 0 which is dependent on “n”.

In one aspect, each R¹ and R² if present, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹³ and R¹² if present, is, independently, a hydrogen, a C₁ toC₃₀ hydrocarbyl, a C₁ to C₃₀ substituted hydrocarbyl, a C₁ to C₃₀halocarbyl, a C₁ to C₃₀ substituted halocarbyl, a halogen, an alkoxide,a sulfide, an amide, a phosphide, a silyl or another anionicheteroatom-containing group; or independently, may join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure.

In another aspect, each R¹ and R² if present, R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹, R¹³ and R¹² if present, independently, a hydrogen, a C₁ toC₁₀ hydrocarbyl, a C₁ to C₁₀ substituted hydrocarbyl, a C₁ to C₁₀halocarbyl, a C₁ to C₁₀ substituted halocarbyl, a halogen, an alkoxide,a sulfide, an amide, a phosphide, a silyl or another anionicheteroatom-containing group; or independently, may join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure.

In still another aspect, each R¹ and R² if present, R³, R⁴, R⁵, R⁶, R⁸,R⁹, R¹⁰, R¹¹, R¹³ and R¹² if present, is, independently, a hydrogen, aC₁ to C₃₀ hydrocarbyl, a C₁ to C₃₀ substituted hydrocarbyl, a C₁ to C₃₀halocarbyl, a C₁ to C₃₀ substituted halocarbyl, a halogen, an alkoxide,a sulfide, an amide, a phosphide, a silyl or another anionicheteroatom-containing group; or independently, may join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure and R⁷ is a hydrogen, aC₃ to C₅₀ hydrocarbyl or a C³ to C₅₀ halocarbyl.

In one aspect, at least one of R⁷ or R¹³ is not a hydrogen atom.

In one embodiment, X can be selected from fluoride, chloride, bromide,iodide, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl,docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl, phenethyl,tolyl, trimethylsilylmethyl, bis(trimethylsilyl)methyl, methoxy, ethoxy,propoxy, butoxy, dimethylamido, diethylamido, methylethylamido, phenoxy,benzoxy, or allyl.

In another embodiment, L can be selected from pyridine, acetonitrile,diethyl ether, tetrahydrofuran, dimethylaniline, trimethylamine,tributylamine, trimethylphosphine, triphenylphosphine, lithium chloride,ethylene, propylene, butene, octene, or styrene.

In specific embodiments of the catalyst compound, R⁷ can be methyl,ethyl n-butyl, t-butyl, benzyl, phenyl 2-methylphenyl, 1-naphthalene,9-phenanthroline, 2-trifluoromethylphenyl, or mesyl, R¹ can be a methyl,R³ can be t-butyl, R¹¹ can be phenyl or t-butyl and various combinationsthereof.

Activators and Catalyst Activation

The catalyst compound can be combined with one or more co-catalysts oractivators. Activators that can be used include alumoxanes such asmethyl alumoxane, modified methyl alumoxane, ethyl alumoxane, iso-butylalumoxane and the like; Lewis acid activators include triphenyl boron,tris-perfluorophenyl boron, tris-perfluorophenyl aluminum and the like;ionic activators include dimethylanilinium tetrakis perfluorophenylborate, triphenyl carbonium tetrakis perfluorophenyl borate,dimethylanilinium tetrakis perfluorophenyl aluminate, and the like.

The alumoxane component useful as an activator typically is anoligomeric aluminum compound represented by the general formula(R^(x)—Al—O)_(n), which is a cyclic compound, or R^(x)(R^(x)—Al—O)_(n)AlR^(x) ₂, which is a linear compound. In the generalalumoxane formula, R^(x) is independently a C₁-C₂₀ alkyl radical, forexample, methyl, ethyl, propyl, butyl, pentyl, isomers thereof, and thelike, and “n” is an integer from 1-50. Most preferably, R^(x) is methyland “n” is at least 4. Methyl alumoxane and modified methyl alumoxanesare most preferred. For further descriptions see, EP 0 279 586, EP 0 594218, EP 0 561 476, W094/10180, and U.S. Pat. Nos. 4,665,208, 4,874,734,4,908,463, 4,924,018, 4,952,540, 4,968,827, 5,041,584, 5,091,352,5,103,031, 5,157,137, 5,204,419, 5,206,199, 5,235,081, 5,248,801,5,329,032, 5,391,793, and 5,416,229.

When an alumoxane or modified alumoxane is used, thecatalyst-precursor-to-activator molar ratio is from about 1:3000 to10:1; alternatively, 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an alumoxane (modifiedor unmodified), some embodiments select the maximum amount of activatorat a 5000-fold molar excess over the catalyst precursor (per metalcatalytic site). The preferred minimum activator-to-catalyst-precursorratio is 1:1 molar ratio.

Ionic activators (at times used in combination with a co-activator) maybe used in the practice of this invention. Preferably, discrete ionicactivators such as [Me₂PhNH][B(C₆F₅)₄], [Ph₃C][B(C₆F₅)₄],[Me₂PhNH][B((C₆H₃-3,5-(CF₃)₂))₄], [Ph₃C][B((C₆H₃-3,5-(CH₃)₂))₄],[NH₄][B(C₆H₅)₄] or Lewis acidic activators such as B(C₆F₅)₃ or B(C₆H₅)₃can be used. Preferred co-activators, when used, are alumoxanes such asmethyl alumoxane, modified alumoxanes such as modified methyl alumoxane,and aluminum alkyls such as tri-isobutyl aluminum, and trimethylaluminum.

An ionizing or stoichiometric activator, neutral or ionic, such astri(n-butyl) ammonium tetrakis(pentafluorophenyl)borate, atrisperfluorophenyl boron metalloid precursor or a trisperfluoronaphthylboron metalloid precursor, polyhalogenated heteroborane anions (WO98/43983), boric acid (U.S. Pat. No. 5,942,459) or combination thereofcan also be used. Examples of neutral stoichiometric activators includetri-substituted boron, aluminum, gallium and indium or mixtures thereof.The three substituent groups are each independently selected fromalkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides,alkoxy and halides. Preferably, the three groups are independentlyselected from halogen, mono or multicyclic (including halosubstituted)aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred arealkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groupshaving 3 to 20 carbon atoms (including substituted aryls). Morepreferably, the three groups are alkyls having 1 to 4 carbon groups,phenyl, naphthyl or mixtures thereof. Even more preferably, the threegroups are halogenated, preferably fluorinated, aryl groups. Mostpreferably, the neutral stoichiometric activator is trisperfluorophenylboron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003,and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299, and 5,502,124, and U.S. Ser. No.08/285,380, filed Aug. 3, 1994, all of which are herein fullyincorporated by reference.

Ionic catalysts can be prepared by reacting a catalyst compound with anactivator, such as B(C₆F₆)₃, which upon reaction with the hydrolyzableligand (X′) of the catalyst compound forms an anion, such as([B(C₆F₅)₃(X′)]⁻), which stabilizes the cationic transition metalspecies generated by the reaction. The catalysts can be, and preferablyare, prepared with activator components which are ionic compounds orcompositions. However preparation of activators utilizing neutralcompounds is also contemplated by this invention.

Compounds useful as an activator component in the preparation of theionic catalyst systems include a cation, which is preferably a Bronstedacid capable of donating a proton, and a compatible non-coordinatinganion which anion is relatively large (bulky), capable of stabilizingthe active catalyst species which is formed when the two compounds arecombined and said anion will be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated substrates or otherneutral Lewis bases such as ethers, nitriles and the like. Two classesof compatible non-coordinating anions have been disclosed in EP-A-0277,003 and EP-A-0 277,004 published 1988: 1) anionic coordinationcomplexes comprising a plurality of lipophilic radicals covalentlycoordinated to and shielding a central charge-bearing metal or metalloidcore, and 2) anions comprising a plurality of boron atoms such ascarboranes, metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L**-H)_(d) ⁺(A^(d−))

wherein L** is an neutral Lewis base;

H is hydrogen;

(L**-H)⁺ is a Bronsted acid;

A^(d−) is a non-coordinating anion having the charge d−; and

d is an integer from 1 to 3.

The cation component, (L**-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from thepre-catalyst after alkylation.

The activating cation (L**-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the alkylated transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L**-H)_(d) ⁺ may also be amoiety such as silver, tropylium, carbeniums, ferroceniums and mixtures,preferably carboniums and ferroceniums; most preferably triphenylcarbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in combination with a co-activator inthe preparation of the improved catalysts of this invention aretri-substituted ammonium salts such as: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(tert-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammoniumsalts such as: di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and other salts such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

Most preferably, the ionic stoichiometric activator (L**-H)_(d) ⁺(A^(d−)) is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

Invention catalyst precursors can also be activated with cocatalysts oractivators that comprise non-coordinating anions containingmetalloid-free cyclopentadienide ions. These are described in US PatentPublication 2002/0058765 A1, published on 16 May 2002, and for theinstant invention, require the addition of a co-activator to thecatalyst pre-cursor.

The term “non-coordinating anion” (NCA) means an anion that does notcoordinate to the catalyst metal cation or that does coordinate to themetal cation, but only weakly. An NCA coordinates weakly enough that aneutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center.“Compatible” non-coordinating anions are those which are not degraded toneutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral catalyst compound and a neutralby-product from the anion. Non-coordinating anions useful in accordancewith this invention are those that are compatible, stabilize thetransition metal complex cation in the sense of balancing its ioniccharge at +1, yet retain sufficient lability to permit displacement byan ethylenically or acetylenically unsaturated monomer duringpolymerization. These types of cocatalysts sometimes use scavengers suchas but not limited to tri-iso-butyl aluminum, tri-n-octyl aluminum,tri-n-hexyl aluminum, triethylaluminum or trimethylaluminum.

Cocatalyst compounds or activator compounds that are initially neutralLewis acids but form a cationic metal complex and a noncoordinatinganion, or a zwitterionic complex upon reaction with the alkylatedcatalyst compounds can also be used. The alkylated invention compound isformed from the reaction of the catalyst pre-cursor and theco-activator. For example, tris(pentafluorophenyl) boron or aluminum actto abstract a hydrocarbyl ligand to yield an invention cationictransition metal complex and stabilizing noncoordinating anion, seeEP-A-0 427 697 and EP-A-0 520 732 for illustrations of analogous Group-4metallocene compounds. Also, see the methods and compounds of EP-A-0 495375. For formation of zwitterionic complexes using analogous Group 4compounds, see U.S. Pat. Nos. 5,624,878, 5,486,632, and 5,527,929.

Additional neutral Lewis-acids are known in the art and are suitable forabstracting formal anionic ligands. See in particular the review articleby E. Y.-X. Chen and T .J. Marks, “Cocatalysts for Metal-CatalyzedOlefin Polymerization: Activators, Activation Processes, andStructure-Activity Relationships”, Chem. Rev., 100, 1391-1434 (2000).

When the cations of noncoordinating anion precursors are Bronsted acidssuch as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation.

When an ionic or neutral stoichiometric activator is used, thecatalyst-precursor-to-activator molar ratio is typically from 1:10 to1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1;1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2. Thecatalyst-precursor-to-co-activator molar ratio is from 1:100 to 100:1;1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1;1:5 to 5:1, 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1, 1:50 to 1:1; 1:25 to1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Preferred activators and activator/co-activator combinations includemethylalumoxane, modified methylalumoxane, mixtures of methylalumoxanewith dimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron, and mixtures of trimethyl aluminum withdimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron.

In some embodiments, scavenging compounds are used with stoichiometricactivators. Typical aluminum or boron alkyl components useful asscavengers are represented by the general formula R^(x)JZ₂ where J isaluminum or boron, R^(x) is a hydrocarbyl group (such as a C1 to C20alkyl), and each Z is independently R^(x) or a different univalentanionic ligand such as halogen (Cl, Br, I), alkoxide (OR^(x)) and thelike. Most preferred aluminum alkyls include triethylaluminum,diethylaluminum chloride, tri-iso-butylaluminum, tri-n-octylaluminum.tri-n-hexylaluminum, trimethylaluminum and the like. Preferred boronalkyls include triethylboron. Scavenging compounds may also bealumoxanes and modified alumoxanes including methylalumoxane andmodified methylalumoxane.

Supported Catalysts

The catalyst compound(s) can be supported or non-supported. To prepareuniform supported catalysts, the catalyst or catalyst precursorpreferably dissolves in the chosen solvent. The term “uniform supportedcatalyst” means that the catalyst, or the catalyst precursor and theactivator, and or the activated catalyst approach uniform distributionupon the support's accessible surface area, including the interior poresurfaces of porous supports. Some embodiments of supported catalystsprefer uniform supported catalysts; other embodiments show no suchpreference.

Invention supported catalyst systems may be prepared by any methodeffective to support other coordination catalyst systems, effectivemeaning that the catalyst so prepared can be used for oligomerizing orpolymerizing olefin in a heterogeneous process. The catalyst precursor,activator, co-activator if needed, suitable solvent, and support may beadded in any order or simultaneously.

By one method, the activator, dissolved in an appropriate solvent suchas toluene may be stirred with the support material for 1 minute to 10hours. The total solution volume may be greater than the pore volume ofthe support, but some embodiments limit the total solution volume belowthat needed to form a gel or slurry (about 90% to 400%, preferably about100% to 200% of the pore volume). The mixture is optionally heated from30° C.-200° C. during this time. The catalyst precursor may be added tothis mixture as a solid, if a suitable solvent is employed in theprevious step, or as a solution. Or alternatively, this mixture can befiltered, and the resulting solid mixed with a catalyst precursorsolution. Similarly, the mixture may be vacuum dried and mixed with acatalyst precursor solution. The resulting catalyst mixture is thenstirred for 1 minute to 10 hours, and the catalyst is either filteredfrom the solution and vacuum dried or evaporation alone removes thesolvent.

Alternatively, the catalyst precursor and activator may be combined insolvent to form a solution. Then the support is added, and the mixtureis stirred for 1 minute to 10 hours. The total solution volume may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 90% to 400%, preferably about 100% to 200% of the pore volume).After stirring, the residual solvent is removed under vacuum, typicallyat ambient temperature and over 10-16 hours. But greater or lesser timesand temperatures are possible.

The catalyst precursor may also be supported absent the activator; inthat case, the activator (and co-activator if needed) is added to apolymerization process's liquid phase. For example, a solution ofcatalyst precursor may be mixed with a support material for a period ofabout 1 minute to 10 hours. The resulting pre-catalyst mixture may befiltered from the solution and dried under vacuum, or evaporation aloneremoves the solvent. The total catalyst-precursor-solution volume may begreater than the support's pore volume, but some embodiments limit thetotal solution volume below that needed to form a gel or slurry (about90% to 400%, preferably about 100% to 200% of the pore volume).

Additionally, two or more different catalyst precursors may be placed onthe same support using any of the support methods disclosed above.Likewise, two or more activators or an activator and co-activator may beplaced on the same support.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Any supportmaterial that has an average particle size greater than 10 μm issuitable for use in this invention. Various embodiments select a poroussupport material, such as for example, talc, inorganic oxides, inorganicchlorides, for example magnesium chloride and resinous support materialssuch as polystyrene polyolefin or polymeric compounds or any otherorganic support material and the like. Some embodiments select inorganicoxide materials as the support material including Group-2, -3, -4, -5,-13, or -14 metal or metalloid oxides. Some embodiments select thecatalyst support materials to include silica, alumina, silica-alumina,and their mixtures. Other inorganic oxides may serve either alone or incombination with the silica, alumina, or silica-alumina. These aremagnesia, titania, zirconia, and the like. Lewis acidic materials suchas montmorillonite and similar clays may also serve as a support. Inthis case, the support can optionally double as the activator component.But additional activator may also be used.

The support material may be pretreated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see for example the descriptions in WO 95/15815 andU.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Invention catalyst carriers may have a surface area of from 10-700 m²/g,a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm.Some embodiments select a surface area of 50-500 m²/g, a pore volume of0.5-3.5 cc/g, or an average particle size of 20-200 μm. Otherembodiments select a surface area of 100-400 m²/g, a pore volume of0.8-3.0 cc/g, and an average particle size of 30-100 μm. Inventioncarriers typically have a pore size of 10-1000 Angstroms, alternatively50-500 Angstroms, or 75-350 Angstroms.

Invention catalysts are generally deposited on the support at a loadinglevel of 10-100 micromoles of catalyst precursor per gram of solidsupport; alternately 20-80 micromoles of catalyst precursor per gram ofsolid support; or 40-60 micromoles of catalyst precursor per gram ofsupport. But greater or lesser values may be used provided that thetotal amount of solid catalyst precursor does not exceed the support'spore volume.

Invention catalysts can be supported for gas-phase, bulk, or slurrypolymerization, or otherwise as needed. Numerous support methods areknown for catalysts in the olefin polymerization art, particularlyalumoxane-activated catalysts; all are suitable for this invention'sbroadest practice. See, for example, U.S. Pat. Nos. 5,057,475 and5,227,440. An example of supported ionic catalysts appears in WO94/03056. U.S. Pat. No. 5,643,847 and WO 96/04319A describe aparticularly effective method. A bulk or slurry process using thisinvention's supported metal complexes activated with alumoxane can beused for ethylene-propylene rubber as described in U.S. Pat. Nos.5,001,205 and 5,229,478. Additionally, those processes suit thisinvention's catalyst systems. Both polymers and inorganic oxides mayserve as supports, as is known in the art. See U.S. Pat. Nos. 5,422,325,5,427,991, 5,498,582, and 5,466,649, and international publications WO93/11172 and WO 94/07928.

Monomers

The catalyst compounds can be used to polymerize or oligomerize anyunsaturated monomer or monomers. Preferred monomers include C₂ to C₁₀₀olefins, preferably C₂ to C₆₀ olefins, preferably C₂ to C₄₀ olefinspreferably C₂ to C₂₀ olefins, preferably C₂ to C₁₂ olefins. In someembodiments preferred monomers include linear, branched or cyclicalpha-olefins, preferably C₂ to C₁₀₀ alpha-olefins, preferably C₂ to C₆₀alpha-olefins, preferably C₂ to C₄₀ alpha-olefins preferably C₂ to C₂₀alpha-olefins, preferably C₂ to C₁₂ alpha-olefins. Preferred olefinmonomers may be one or more of ethylene, propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1,3-methylpentene-1, 3,5,5-trimethylhexene-1, and 5-ethylnonene-1.

In another embodiment the polymer produced herein is a copolymer of oneor more linear or branched C₃ to C₃₀ prochiral alpha-olefins or C₅ toC₃₀ ring containing olefins or combinations thereof capable of beingpolymerized by either stereospecific and non-stereospecific catalysts.Prochiral, as used herein, refers to monomers that favor the formationof isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

Preferred monomers may also include aromatic-group-containing monomerscontaining up to 30 carbon atoms. Suitable aromatic-group-containingmonomers comprise at least one aromatic structure, preferably from oneto three, more preferably a phenyl, indenyl, fluorenyl, or naphthylmoiety. The aromatic-group-containing monomer further comprises at leastone polymerizable double bond such that after polymerization, thearomatic structure will be pendant from the polymer backbone. Thearomatic-group containing monomer may further be substituted with one ormore hydrocarbyl groups including but not limited to C₁ to C₁₀ alkylgroups. Additionally two adjacent substitutions may be joined to form aring structure. Preferred aromatic-group-containing monomers contain atleast one aromatic structure appended to a polymerizable olefinicmoiety. Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,para-methylstyrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C₁ to C₁₀ alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,cyclopentadiene, cyclopentene, 4-methylcyclopentene, cyclohexene,4-methylcyclohexene, cyclobutene, vinyladamantane, norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5-butylylnorbornene, 5-pentylnorbornene, 5-hexylnorbornene,5-heptylnorbornene, 5-octylnorbornene, 5-nonylnorbornene,5-decylnorbornene, 5-phenylnorbornene, vinylnorbornene, ethylidenenorbornene, 5,6-dimethylnorbornene, 5,6-dibutylnorbornene and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least one, typically two, of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). It is furtherpreferred that the diolefin monomers be selected from alpha-omega-dienemonomers (i.e. di-vinyl monomers). More preferably, the diolefinmonomers are linear di-vinyl monomers, most preferably those containingfrom 4 to 30 carbon atoms. Examples of preferred dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, particularly preferreddienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Non-limiting examples of preferred polar unsaturated monomers useful inthis invention, particularly with group 4 and 6 metal compounds, includenitro substituted monomers including 6-nitro-1-hexene; amine substitutedmonomers including N-methylallylamine, N-allylcyclopentylamine, andN-allyl-hexylamine; ketone substituted monomers including methyl vinylketone, ethyl vinyl ketone, and 5-hexen-2-one; aldehyde substitutedmonomers including acrolein, 2,2-dimethyl-4-pentenal, undecylenicaldehyde, and 2,4-dimethyl-2,6-heptadienal; alcohol substituted monomersincluding allyl alcohol, 7-octen-1-ol, 7-octene-1,2-diol,10-undecen-1-ol, 10-undecene-1,2-diol, 2-methyl-3-buten-1-ol; acetal,epoxide and or ether substituted monomers including4-hex-5-enyl-2,2-dimethyl-[1,3]dioxolane,2,2-dimethyl-4-non-8-enyl-[1,3]dioxolane, acrolein dimethyl acetal,butadiene monoxide, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene,1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, allyl glycidyl ether,2,5-dihydrofuran, 2-cyclopenten-1-one ethylene ketal,11-methoxyundec-1-ene, and 8-methoxyoct-1-ene; sulfur containingmonomers including allyl disulfide; acid and ester substituted monomersincluding acrylic acid, vinylacetic acid, 4-pentenoic acid,2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoicacid, 2,6-heptadienoic acid, methyl acrylate, ethyl acrylate, tert-butylacrylate, n-butyl acrylate, methacrylic acid, methyl methacrylate, ethylmethacrylate, tert-butyl methacrylate, n-butyl methacrylate,hydroxypropyl acrylate, acetic acid oct-7-enyl ester, non-8-enoic acidmethyl ester, acetic acid undec-10-enyl ester, dodec-11-enoic acidmethyl ester, propionic acid undec-10-enyl ester, dodec-11-enoic acidethyl ester, and nonylphenoxypolyetheroxy acrylate; siloxy containingmonomers including trimethyloct-7-enyloxy silane, andtrimethylundec-10-enyloxy silane, polar functionalized norbornenemonomers including 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid,cis-5-norbornene-endo-2,3-dicarboxylic acid,5-norbornene-2,2,-dimethanol, cis-5-norbornene-endo-2,3-dicarboxylicanhydride, 5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-methanol,5-norbornene-2-ol, 5-norbornene-2-yl acetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, 2-acetyl-5-norbornene, 7-synmethoxymethyl-5-norbornen-2-one, 5-norbornen-2-ol, and5-norbornen-2-yloxy-trimethylsilane, and partially fluorinated monomersincluding nonafluoro-1-hexene, allyl-1,1,2,2,-tetrafluoroethyl ether,2,2,3,3-tetrafluoro-non-8-enoic acid ethyl ester,1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-oct-7-enyloxy)-ethanesulfonylfluoride, acrylic acid2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-octyl ester, and1,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4-octafluoro-dec-9-enyloxy)-ethanesulfonylfluoride.

In an embodiment herein, the process described herein is used to producean oligomer of any of the monomers listed above. Preferred oligomersinclude oligomers of any C₂ to C₂₀ olefins, preferably C₂ to C₁₂alpha-olefins, most preferably oligomers comprising ethylene, propyleneand or butene are prepared. A preferred feedstock for theoligomerization process is the alpha-olefin, ethylene. But otheralpha-olefins, including but not limited to propylene and 1-butene, mayalso be used alone or combined with ethylene. Preferred alpha-olefinsinclude any C₂ to C₄₀ alpha-olefin, preferably and C₂ to C₂₀alpha-olefin, preferably any C₂ to C₁₂ alpha-olefin, preferablyethylene, propylene, and butene, most preferably ethylene. Dienes may beused in the processes described herein, preferably alpha-omega-dienesare used alone or in combination with mono-alpha olefins.

In a preferred embodiment the process described herein may be used toproduce homopolymers or copolymers. For the purposes of this inventionand the claims thereto a copolymer may comprise two, three, four or moredifferent monomer units. Preferred polymers produced herein includehomopolymers or copolymers of any of the above monomers. In a preferredembodiment the polymer is a homopolymer of any C₂ to C₁₂ alpha-olefin.Preferably the polymer is a homopolymer of ethylene or a homopolymer ofpropylene. In another embodiment the polymer is a copolymer comprisingethylene and one or more of any of the monomers listed above. In anotherembodiment the polymer is a copolymer comprising propylene and one ormore of any of the monomers listed above. In another preferredembodiment the homopolymers or copolymers described, additionallycomprise one or more diolefin comonomers, preferably one or more C₄ toC₄₀ diolefins.

In another preferred embodiment the polymer produced herein is acopolymer of ethylene and one or more C₃ to C₂₀ linear, branched orcyclic monomers, preferably one or more C₃ to C₁₂ linear, branched orcyclic alpha-olefins. Preferably the polymer produced herein is acopolymer of ethylene and one or more of propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1,3-methylpentene-1, 3,5,5-trimethylhexene-1, cyclopentene,4-methylcyclopentene, cyclohexene, and 4-methylcyclohexene.

In another preferred embodiment the polymer produced herein is acopolymer of propylene and one or more C₂ or C₄ to C₂₀ linear, branchedor cyclic monomers, preferably one or more C₂ or C₄ to C₁₂ linear,branched or cyclic alpha-olefins. Preferably the polymer produced hereinis a copolymer of propylene and one or more of ethylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1, 3-methylpentene-1, and 3,5,5-trimethylhexene-1.

In a preferred embodiment, the polymer produced herein is a homopolymerof norbornene or a copolymer of norbornene and a substituted norbornene,including polar functionalized norbornenes.

In a preferred embodiment the copolymers described herein comprise atleast 50 mole % of a first monomer and up to 50 mole % of othermonomers.

In another embodiment, the polymer comprises a first monomer present atfrom 40 to 95 mole %, preferably 50 to 90 mole %, preferably 60 to 80mole %, and a comonomer present at from 5 to 60 mole %, preferably 10 to40 mole %, more preferably 20 to 40 mole %, and a termonomer present atfrom 0 to 10 mole %, more preferably from 0.5 to 5 mole %, morepreferably 1 to 3 mole %.

In a preferred embodiment the first monomer comprises one or more of anyC₃ to C₈ linear branched or cyclic alpha-olefins, including propylene,butene, (and all isomers thereof), pentene (and all isomers thereof),hexene (and all isomers thereof), heptene (and all isomers thereof), andoctene (and all isomers thereof). Preferred monomers include propylene,1-butene, 1-hexene, 1-octene, cyclopentene, cyclohexene, cyclooctene,hexadiene, cyclohexadiene and the like.

In a preferred embodiment the comonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the termonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins, (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the polymers described above further compriseone or more dienes at up to 10 wt %, preferably at 0.00001 to 1.0 wt %,preferably 0.002 to 0.5 wt %, even more preferably 0.003 to 0.2 wt %,based upon the total weight of the composition. In some embodiments 500ppm or less of diene is added to the polymerization, preferably 400 ppmor less, preferably or 300 ppm or less. In other embodiments at least 50ppm of diene is added to the polymerization, or 100 ppm or more, or 150ppm or more.

Polymerization Processes

The catalyst compounds can be used to polymerize and/or oligomerize oneor more monomers using any one or more solution, slurry, gas-phase, andhigh-pressure polymerization processes. The catalyst compound andoptional co-catalyst(s), can be delivered as a solution or slurry,either separately to a reactor, activated in-line just prior to areactor, or preactivated and pumped as an activated solution or slurryto a reactor. Polymerizations can be carried out in either singlereactor operations, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operations, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to firstreaction and another component to other reactors. In one preferredembodiment, the pre-catalyst is activated in the reactor in the presenceof olefin.

The catalyst compositions can be used individually or can be mixed withother known polymerization catalysts to prepare polymer blends. Monomerand catalyst selection allows polymer blend preparation under conditionsanalogous to those using individual catalysts. Polymers having increasedMWD for improved processing and other traditional benefits availablefrom polymers made with mixed catalyst systems can thus be achieved.

One or more scavenging compounds can be used. Here, the term scavengingcompound means a compound that removes polar impurities from thereaction environment. These impurities adversely affect catalystactivity and stability. Typically, purifying steps are usually usedbefore introducing reaction components to a reaction vessel. But suchsteps will rarely allow polymerization without using some scavengingcompounds. Normally, the polymerization process will still use at leastsmall amounts of scavenging compounds.

Typically, the scavenging compound will be an organometallic compoundsuch as the Group-13 organometallic compounds of U.S. Pat. Nos.5,153,157, 5,241,025, and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132,and that of WO 95/07941. Exemplary compounds include triethyl aluminum,triethyl borane, tri-iso-butyl aluminum, methyl alumoxane, iso-butylalumoxane, and tri-n-octyl aluminum. Those scavenging compounds havingbulky or C₆-C₂₀ linear hydrocarbyl substituents connected to the metalor metalloid center usually minimize adverse interaction with the activecatalyst. Examples include triethylaluminum, but more preferably, bulkycompounds such as tri-iso-butyl aluminum, tri-iso-propyl aluminum, andlong-chain linear alkyl-substituted aluminum compounds, such astri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum.When alumoxane is used as the activator, any excess over that needed foractivation will scavenge impurities and additional scavenging compoundsmay be unnecessary. Alumoxanes also may be added in scavengingquantities with other activators, e.g., methylalumoxane,[Me₂HNPh]⁺[B(pfp)₄]⁻ or B(pfp)₃ (perfluorophenyl=pfp=C₆F₅).

In terms of polymer density, the polymers capable of production inaccordance the invention, can range from about 0.85 to about 0.95,preferably from 0.87 to 0.93, more preferably 0.89 to 0.920. Polymermolecular weights can range from about 50,000 Mn to about 2,000,000 Mnor greater. Molecular weight distributions can range from about 1.1 toabout 50.0, with molecular weight distributions from 1.2 to about 5.0being more typical. Pigments, antioxidants and other additives, as isknown in the art, may be added to the polymer.

Gas Phase Polymerization

Generally, in a fluidized gas bed process for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream can be withdrawn from the fluidized bedand recycled back into the reactor. Simultaneously, polymer product canbe withdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See for example U.S. Pat. Nos. 4,543,399,4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616,661, and 5,668,228 all of which are fullyincorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment when high density polyethylene is desired then the reactortemperature is typically between 70° C. and 105° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the partial pressure of the main monomer. Thepreferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 to 90 mole percent and thecomonomer partial pressure is in the range of from about 138 kPa toabout 517 kPa, preferably about 517 kPa to about 2069 kPa, which aretypical conditions in a gas phase polymerization process. Also in somesystems the presence of comonomer can increase productivity.

In a preferred embodiment, the reactor utilized in the present inventionis capable of producing more than 500 lbs of polymer per hour (227Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher, preferablygreater than 1000 lbs/hr (455 Kg/hr), more preferably greater than10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr(15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr(22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr)to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over100,000 lbs/hr (45,500 Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818, and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202, andEP-B-0 634 421 all of which are herein fully incorporated by reference.

In another preferred embodiment the catalyst system is in liquid formand is introduced into the gas phase reactor into a resin particle leanzone. For information on how to introduce a liquid catalyst system intoa fluidized bed polymerization into a particle lean zone, please seeU.S. Pat. No. 5,693,727, which is incorporated by reference herein.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psig to 735 psig, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process should be operatedabove the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at a pressure of 3620 kPa to 4309 kPa and at a temperature inthe range of about 60° C. to about 104° C. depending on the desiredpolymer melting characteristics. Reaction heat is removed through theloop wall since much of the reactor is in the form of a double jacketedpipe. The slurry is allowed to exit the reactor at regular intervals orcontinuously to a heated low pressure flash vessel, rotary dryer and anitrogen purge column in sequence for removal of the isobutane diluentand all unreacted monomer and comonomers. The resulting hydrocarbon freepowder is then compounded for use in various applications.

In another embodiment, the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of predominant monomer in the reactor liquid medium is inthe range of from about 1 to 10 wt %, preferably from about 2 to about 7wt %, more preferably from about 2.5 to about 6 wt %, most preferablyfrom about 3 to about 6 wt %.

Another process of the invention is where the process, preferably aslurry or gas phase process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-iso-butylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described in PCTpublication WO 96/08520 and U.S. Pat. No. 5,712,352, which are hereinfully incorporated by reference.

In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-iso-butyl aluminum and anexcess of alumoxane or modified alumoxane.

Homogeneous, Bulk or Solution Phase Polymerization

The catalysts described herein can be used advantageously in homogeneoussolution processes. Generally this involves polymerization in acontinuous reactor in which the polymer formed and the starting monomerand catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent.

Temperature control in the reactor is obtained by balancing the heat ofpolymerization and with reactor cooling by reactor jackets or coolingcoils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature depends onthe catalyst used. In general, the reactor temperature preferably canvary between about 0° C. and about 160° C., more preferably from about10° C. to about 140° C., and most preferably from about 40° C. to about120° C. In series operation, the second reactor temperature ispreferably higher than the first reactor temperature. In parallelreactor operation, the temperatures of the two reactors are independent.The pressure can vary from about 1 mm Hg to 2500 bar (25,000 MPa),preferably from 0.1 bar to 1600 bar (1-16,000 MPa), most preferably from1.0 to 500 bar (10-5000 MPa).

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor, or plug flow reactor, or more than one reactor operatedin series or parallel. These reactors may have or may not have internalcooling and the monomer feed may or may not be refrigerated. See thegeneral disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See also, international application WO 96/33227 and WO97/22639.

Medium and High Pressure Polymerizations

In the high pressure process for the polymerization of ethylene alone orin combination with C₃ to C₁₀ alpha-olefins and optionally othercopolymerizable olefins, the temperature of the medium within which thepolymerization reaction occurs is at least 120° C. and preferably above140° C. and may range to 350° C., but below the decompositiontemperature of said polymer product, typically from 310° C. to 325° C.Preferably, the polymerization is completed at a temperature within therange of 130° C. to 230° C. The polymerization is completed at apressure above 200 bar (20 MPa), and generally at a pressure within therange of 500 bar (50 MPa) to 3500 bar (350 MPa). Preferably, thepolymerization is completed at a pressure within the range from 800 bar(80 MPa) to 2500 bar (250 MPa).

For medium pressure process, the temperature within which thepolymerization reaction occurs is at least 80° C. and ranges from 80° C.to 250° C., preferably from 100° C. to 220° C., and should for a givenpolymer in the reactor, be above the melting point of said polymer so asto maintain the fluidity of the polymer-rich phase. The pressure can bevaried between 100 and 1000 bar for ethylene homopolymers and from 30bar (3 MPa) to 1000 bar (100 MPa), especially 50 bar (5 MPa) to 500 bar(50 MPa) for processes producing ethylene copolymers containing C₃ toC₁₀ olefins and optionally other copolymerizable olefins.

More recently, polymerization conditions for high pressure and ortemperature polymerizations to prepare propylene homopolymers andcopolymers of propylene with C₃ to C₁₀ olefins and optionally othercopolymerizable olefins have been reported. See U.S. Ser. No. 60/431,185filed Dec. 5, 2002; U.S. Ser. No. 60/431,077, filed Dec. 5, 2002; andU.S. Ser. No. 60/412,541, filed Sep. 20, 2002.

After polymerization and deactivation of the catalyst, the polymerproduct can be recovered by processes well known in the art. Any excessreactants may be flashed off from the polymer and the polymer obtainedextruded into water and cut into pellets or other suitable comminutedshapes. For general process conditions, see the general disclosure ofU.S. Pat. Nos. 5,084,534, 5,408,017, 6,127,497, and 6,255,410 which areincorporated herein by reference.

This invention further relates to

1. A transition metal catalyst compound represented by one of thestructures depicted above as Formula A, B, C, D or E: wherein: each Xis, independently, a hydride, a halogen, a hydrocarbyl, a substitutedhydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is 0, 1, 2 or3; each R¹ and R² if present, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³and R¹² if present, is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, ahalogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl oranother anionic heteroatom-containing group, or independently, may jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure; L is aneutral ligand bonded to M that may include molecules such as but notlimited to pyridine, acetonitrile, diethyl ether, tetrahydrofuran,dimethylaniline, trimethylamine, tributylamine, trimethylphosphine,triphenylphosphine, lithium chloride, ethylene, propylene, butene,octene, styrene, and the like; M is Hf, Zr or Ti; m is 0, 1 or 2 andindicates the absence or presence of L; and n is 1 or 2.

2. The compound according to paragraph 1, wherein the structure is C.

3. The compound according to either of paragraphs 1 or 2, wherein n is 1and w is 2 or 3.

4. The compound according to any of paragraphs 1 through 3, wherein R⁷is methyl, ethyl n-butyl, t-butyl, benzyl, phenyl 2-methylphenyl,1-naphthalene, 9-phenanthroline, 2-trifluoromethylphenyl, or mesyl.

5. The compound according to paragraph 1, wherein n is 1 and thestructure is one of the structures depicted above as Formula A¹, B¹, C¹,D¹ or E¹, wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, L, M, and m are as defined in paragraph 1, Me is methyl and w is 2or 3.

6. A transition metal catalyst composition comprising an activator andthe compound of paragraph 1, 2, 3, 4 or 5.

7. The composition according to paragraph 6, wherein the structure is C.

8. The composition according to either of paragraphs 6 or 7, wherein nis 1 and w is 2 or 3.

9. The composition according to any of paragraphs 6 through 8, whereinR⁷ is methyl, ethyl n-butyl, t-butyl, benzyl, phenyl 2-methylphenyl,1-naphthalene, 9-phenanthroline, 2-trifluoromethylphenyl, or mesyl.

10. The composition according to paragraph 1, wherein n is 1 and thestructure is one of the structures depicted above as Formula A¹, B¹, C¹,D¹ or E¹, wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, L, M, and m are as defined in paragraph 1, Me is methyl and w is 2or 3.

11. A process for polymerization comprising:

-   contacting one or more olefins (such as ethylene and optionally one    or more unsaturated monomers) with the catalyst compound of any of    paragraphs 1-10.

12. The process according to paragraph 11, wherein the structure is C.

13. The process according to either of paragraphs 11 or 12, wherein n is1 and w is 2 or 3.

14. The process according to any of paragraphs 11 through 13, wherein R⁷is methyl, ethyl n-butyl, t-butyl, benzyl, phenyl 2-methylphenyl,1-naphthalene, 9-phenanthroline, 2-trifluoromethylphenyl, or mesyl.

15. The process according to paragraph 11, wherein n is 1 and thestructure is one of the structures depicted above as Formula A¹, B¹, C¹,D¹ or E¹, wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, L, M, and m are as defined in paragraph 1, Me is methyl and w is 2or 3.

16. A process for polymerization comprising:

-   contacting one or more olefins (such as ethylene and optionally one    or more unsaturated monomers) with a transition metal catalyst    composition comprising an activator and the compound of any of    claims 1 to 10.

17. The process according to paragraph 16, wherein the structure is C.

18. The process according to either of paragraphs 16 or 17, wherein n is1 and w is 2 or 3.

19. The process according to any of paragraphs 16 through 18, wherein R⁷is methyl, ethyl n-butyl, t-butyl, benzyl, phenyl 2-methylphenyl,1-naphthalene, 9-phenanthroline, 2-trifluoromethylphenyl, or mesityl.

20. The process according to paragraph 16, wherein n is 1 and thestructure is one of the structures depicted above as Formula A¹, B¹, C¹,D¹ or E¹, wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,R¹³, L, M, and m are as defined in paragraph 1, Me is methyl and w is 2or 3.

21. A compound comprising a formula:

wherein

each R¹ and R² if present R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹³ andR¹² if present is independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, ahalogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl oranother anionic heteroatom-containing group, or independently, may jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure,provided R⁷ is not methyl when R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹² areeach hydrogen atoms in formula (II), R⁷ and R³ are not both methyl whenR⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹² are each hydrogen atoms in formula(III) and R⁷ is not a hydrogen atom when R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹⁰,R¹¹, R¹² are each hydrogen atoms in formula (IV).

22. The compound according to paragraph 21, wherein R¹ is a hydrogenatom or methyl, R², R³, R⁴, R⁵, R⁶ are all hydrogen atoms, R⁷ is methyl,ethyl, butyl, benzyl, phenyl, 2-methylphenyl, 1-naphthyl or9-phenanthryl and R⁸, R⁹, R¹⁰, R¹¹, and R¹² are all hydrogen atoms informula (I).

23. The compound according to paragraph 21, wherein R³, R⁴, R⁵, R⁶, R⁸,R⁹, R¹⁰, R¹¹ and R¹² are all hydrogen atoms and R⁷ is t-butyl, benzyl,butyl, methyl, ethyl, phenyl, 1-naphthyl, 9-phenanthryl,2-trifluoromethylphenyl or mesityl in formula (II).

24. The compound according to paragraph 21, wherein R³ is a hydrogenatom or a methyl, R⁵ is a methyl, R⁷ is a benzyl or phenyl and R⁴, R⁵,R⁶, R⁸, R⁹ R¹⁰ and R¹¹ are all hydrogen atoms in formula (III).

25. The compound according to paragraph 21, wherein R⁷ is a methyl, R³,R⁴, R⁵, R⁶, R⁸, R⁹ R¹⁰ and R¹² are all hydrogen atoms and R¹¹ is phenylor t-butyl in formulae (IV) or (V).

26. The compound, composition or process according to any of paragraphs1 through 25, wherein at least one of R⁷ or R¹³ is not a hydrogen atom.

27. The process according to any of paragraphs 16 through 20, whereinthe polymer is homopolyethylene.

28. The compound, composition or process according to any of paragraphs1 through 20, wherein when R¹² is a hydrogen atom for structure A, A¹, Bor B¹, M may react with the R¹² hydrogen atom to generate HX and a bondis formed between the carbon bearing position at R¹² and M.

The following abbreviations are used through this specification: Me ismethyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pris normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl,p-tBu is para-tertiary butyl, nBu is normal butyl, TMS istrimethylsilyl, TIBA is trisobutylaluminum, MAO is methylalumoxane, pMeis para-methyl, Ar* is 2,6-diisopropylaryl, Bz is benzyl, THF istetrahydrofuran, RT is room temperature and tol is toluene.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. Illustrative catalyst compounds, eachaccording to one or more embodiments described, were synthesized andused to polymerize ethylene monomer. All reactions were carried outunder a purified nitrogen atmosphere using standard glovebox, highvacuum or Schlenk techniques, unless otherwise noted. All solvents usedwere anhydrous, de-oxygenated and purified according to knownprocedures. All starting materials were either purchased from Aldrichand purified prior to use or prepared according to procedures known tothose skilled in the art.

N-(1-Phenylethyl)quinolin-8-amine (A1): A mixture of 1.44 g (10.0 mmol)of 8-aminoquinoline, 1.01 g (10.0 mmol) of triethylamine and 1.85 g(10.0 mmol) of 1-bromo-1-phenylethane (1) was stirred for 2 hr at 120°C. One more portion of 1.01 g of triethylamine as well as 1.85 g of1-bromo-1-phenylethane was added. The resulting mixture was stirred foradditional 2 hr at 120° C. One more portion of triethylamine and1-bromo-1-phenylethane was added, and the reaction mixture was stirredfor 2 hr at 120° C. Finally, the product was isolated using flashchromatography on silica gel 60 (40-63 um, eluent: hexanes-ethylacetate=20:1, vol.) to give 2.26 g (91%) of the title compound.

1,2-Diphenylethanol (3): To 100 mL (0.10 mol) of 1.0 M BnMgBr in THF9.50 g (90 mmol) of benzaldehyde (2) was added with vigorous stirring at−10° C. This mixture was slowly warmed to room temperature and thenstirred for 2 hr at this temperature. The mixture was added to 300 mL ofsaturated aqueous Na₂SO₄. The organic layer was separated and washedwith saturated aqueous NH₄Cl. The aqueous layer was extracted with 2×100mL of diethyl ether. The combined organic extracts were evaporated todryness, and the residue was dissolved in 100 mL of dichloromethane. Theobtained solution was dried over Na₂SO₄ and evaporated to dryness. Thiscrude product was further used without an additional purification. Yield12.0 g (67%) of the title compound.

1,1′-(1-Bromoethane-1,2-diyl)dibenzene (4): To a solution of 12.0 (60.5mmol) of 1,2-diphenylethanol in 50 mL of dry diethyl ether, 11.0 g (3.80mL, 40.0 mmol) of PBr₃ was added with vigorous stirring at −10° C. Theresulting mixture was stirred for 12 hr at room temperature and thenadded to 350 mL of cold water. The organic layer was separated, and theaqueous layer was extracted with 2×100 mL of water. The combined organicextracts were washed with aqueous NaHCO₃, dried over Na₂SO₄, andevaporated to dryness. This procedure gave 13.2 g (84%) of the titleproduct.

N-(1,2-Diphenylethyl)-2-methylquinolin-8-amine (A2): A mixture of 2.05 g(13.0 mmol) of 2-methyl-8-aminoquinoline, 2.53 g (25 mmol) oftriethylamine and 6.50 g (25 mmol) of 4 was stirred for 2 hr at 120° C.The product was isolated using flash chromatography on silica gel 60(40-63 um, eluent: hexanes-ethyl acetate =20:1, vol.) to generated 3.67(87%) of A2.

(2-Methylphenyl)(phenyl)methanol (5): To the Grignard reagent obtainedfrom 29.0 g (0.17 mol) of ortho-bromotoluene and 5.0 g (0.20 mol) ofmagnesium turnings in 170 mL of THF, 15.9 g (0.15 mol) of benzaldehydewas added with vigorous stirring at 0° C. The resulting mixture wasstirred for 2 hr at room temperature. This mixture was added to 300 mLof saturated aqueous Na₂SO₄. The organic layer was separated and washedwith saturated aqueous NH₄Cl. The aqueous layer was extracted with 3×200mL of ether. The combined organic extracts were evaporated to dryness,and the residue was dissolved in 200 mL of dichloromethane. The obtainedsolution was dried over Na₂SO₄ and evaporated to dryness. This crudeproduct was further used without additional purification. Yield 28.1 g(94%) of 5.

1-[Bromo(phenyl)methyl]-2-methylbenzene (6): To a solution of 28.1 g(140 mmol) of 5 in 150 mL of dry diethyl ether, 25.6 g (8.89 mL, 94.4mmol) of PBr₃ was added at −10° C. The resulting mixture was stirred for12 hr at room temperature and then added to 450 mL of cold water. Theorganic layer was separated, and the aqueous layer was extracted with2×150 mL of water. The combined organic extracts were washed withaqueous NaHCO₃, dried over Na₂SO₄, and then evaporated to dryness. Thisprocedure gave 33.0 g (89%) of the title product.

N-[(2-Methylphenyl)(phenyl)methyl]quinolin-8-amine (A3): A mixture of4.75 g (33 mmol) of 8-aminoquinoline, 3.03 g (30 mmol) of triethylamineand 7.85 g (30 mmol) of 6 was stirred for 2 hr at 120° C. One moreportion of 3.03 g of triethylamine as well as 7.85 g of 6 was added. Theresulting mixture was stirred for additional 2 hr at 120° C. Next, onemore portion of triethylamine and 6 were added, and the reaction mixturewas stirred for 2 hr at 120° C. Finally, the product was isolated usingflash chromatography on silica gel 60 (40-63 um, eluent: hexanes-ethylacetate=20:1, vol.). Yield 2.78 g (26%).

2-Methyl-N-[(2-methylphenyl)(phenyl)methyl]quinolin-8-amine (A4): Amixture of 5.20 g (33 mmol) of 2-methyl-8-aminoquinoline, 3.03 g (30mmol) of triethylamine and 7.85 g (30 mmol) of1-[bromo(phenyl)methyl]-2-methylbenzene was stirred for 2 hr at 120° C.One more portion of 3.03 g of triethylamine as well as 7.85 g of1-[bromo(phenyl)methyl]-2-methylbenzene was added. The resulting mixturewas stirred for additional 2 hr at 120° C. Finally, the product wasisolated using flash chromatography on silica gel 60 (40-63 um, eluent:hexanes-ethyl acetate=20:1, vol.) to generate 1.82 g (17%) of the titlecompound A4.

1-Naphthyl(phenyl)methanol (7): To the Grignard reagent obtained from33.1 g (0.16 mol) of 1-bromonaphthalene and 4.62 g (0.19 mol) ofmagnesium turnings in 160 mL of THF, 15.9 g (0.15 mol) of benzaldehydewas added with vigorous stirring at 0° C. The resulting mixture wasstirred for 2 hr at room temperature. This mixture was added to 300 mLof saturated aqueous Na₂SO₄. The organic layer was separated and washedwith saturated aqueous NH₄Cl. The aqueous layer was extracted with 2×200mL of diethyl ether. The combined organic extracts were evaporated todryness, and the residue was dissolved in 150 mL of dichloromethane. Theobtained solution was dried over Na₂SO₄, and then evaporated to dryness.This crude product was further used without an additional purification.Yield 32.3 g (91%) of the title compound.

1-[Bromo(phenyl)methyl]naphthalene (8): To a solution of 32.3 g (138mmol) of 7 in 150 mL of dry diethyl ether, 24.8 g (8.62 mL, 91.6 mmol)of PBr₃ was added at −10° C. The resulting mixture was stirred for 12 hrat room temperature and then added to 450 mL of cold water. The organiclayer was separated, and the aqueous layer was extracted with 2×150 mLof water. The combined organic extracts were washed with aqueous NaHCO₃,dried over Na₂SO₄, and then evaporated to dryness. This procedure gave37.7 g (92%) of 8.

2-Methyl-N-[1-naphthyl(phenyl)methyl]quinolin-8-amine (A5): A mixture of2.05 g (13.0 mmol) of 2-methyl-8-aminoquinoline, 2.53 g (25 mmol) oftriethylamine and 7.43 g (25 mmol) of 8 was stirred for 2 hr at 120° C.One more portion of 2.53 g of triethylamine as well as 7.43 g of 8 wasadded. The resulting mixture was stirred for additional 2 hr at 120° C.Finally, the product was isolated using flash chromatography on silicagel 60 (40-63 um, eluent: hexanes-ethyl acetate=20:1, vol.) to give 0.56g (12%) of the title compound A5.

2-Methoxy-N-[(1E)-phenylmethylene]aniline (9): A mixture of 31.8 g (0.30mol) of benzaldehyde, 36.9 g (0.30 g) of 2-methoxyaniline and 450 mL oftoluene was refluxed using a Dean-Stark head for 1 hr. 15 granules of 4Amolecular sieves were added. This mixture was refluxed for 4 hr, thenfiltered off, and the filtrate was evaporated to dryness. The residuewas dried in vacuum at 70° C. This crude product was further usedwithout an additional purification, since it is unstable on silica gel60 and decomposes when dried under vacuum. Yield 52.0 g (82%) of thetitle material.

N-(2,2-Dimethyl-1-phenylpropyl)-2-methoxyaniline (B1): To a solution of1.27 g (6.00 mmol) of 9 in 40 mL of THF, 4.20 mL (6.30 mmol) of 1.5 M^(t)BuLi in pentane was added with vigorous stirring at −80° C. Themixture was slowly warmed to room temperature, and then 2 mL of waterwas added. The resulting mixture was evaporated to dryness. The productwas isolated by flash chromatography on silica gel 60 (40-63 um, eluent:from hexanes to hexanes-diethyl ether=40:1, vol.) to yield 1.50 g (93%)of B1.

2-Methoxy-N-[9-phenanthryl(phenyl)methyl]aniline (B2): To a solution of5.14 g (20.0 mmol) of 9-bromophenanthrene in 80 mL of THF, 26.7 mL (40.1mmol) of 1.5 M ^(t)BuLi in pentane was added with vigorous stirring at−80° C. This mixture was additionally stirred for 1 hr at thistemperature and then slowly warmed to room temperature. The resultingmixture was stirred for 30 min at ambient temperature and then cooled to−80° C. A solution of 4.22 g (20.0 mol) of 9 in 50 mL of THF was added.To the resulting mixture, 5 mL of water was added, and then this mixturewas evaporated to dryness. The title product was isolated by flashchromatography on silica gel 60 (40-63 um, eluent: from hexanes tohexanes-diethyl ether=40:1, vol.). Yield 7.32 g (94%).

N-(1,2-Diphenylethyl)-2-methoxyaniline (B3): To a solution of 4.22 g(20.0 mmol) of 9 in 50 mL of THF, 48.0 mL (26.0 mmol) of 0.55 M BnMgClin THF was added with vigorous stirring at −80° C. This mixture wasslowly warmed to room temperature, and then 2 mL of water was added. Theresulting mixture was evaporated to dryness. The product was isolated byflash chromatography on silica gel 60 (40-63 um, eluent: from hexanes tohexanes-diethyl ether=40:1, vol.) to give 5.83 g (96%) of B3.

2-Phenoxy-5-methyl-N-[(1E)-2-pyridylmethylene]aniline (11): To a slurryof 2-amino-4-methylphenol (4.40 g, 35.7 mmol) in 300 mL water, a watersolution of pyridine-2-carbaldehyde (3.80 g, 35.5 mmol) was slowlyadded, forming a yellow slurry. After stirring overnight, the suspensionwas poured through a frit and the solid washed with water. The orangesolid was dissolved in 300 mL CH₂Cl₂ and extracted with 3×100 mL water,dried over MgSO₄ and filtered to give a red solution. The solvent wasremoved under vacuum to give a red oil. The oil was re-dissolved inCH₂Cl₂, layered with an equal volume of hexane and cooled to −35° C. toyield yellow crystals of 11(5.56 g, 73% yield).

2-Phenoxy-3-tert-butyl-5-methyl-N-[(1E)-2-pyridylmethylene]aniline (12):To a slurry of 2-amino-4-methyl-6-tertbutylphenol (0.70 g, 3.90 mmol) in5 mL methanol, a methanol solution of pyridine-2-carbaldehyde (0.418 g,3.90 mmol) was slowly added, forming a dark orange solution. Two dropsformic acid were added, quickly forming a yellow precipitate. This wasstirred for 2 hr, then collected on a frit, washed with cold methanoland dried under vacuum to yield 0.72 g of 12 (69%).

2-Phenoxy-5-methyl-N-[phenyl(2-pyridyl)methyl]aniline (C1): To asolution of 12 (300 mg, 1.12 mmol) in THF was added 1.24 mL of a 1.8M^(n)Bu₂O solution of phenyl lithium at −40° C. After stirring for 15min, the reaction was quenched with water (1 mL). MgSO₄ was added andthe mixture filtered to give a yellow solution. Removal of the solventunder vacuum gave C1 as a yellow oil (240 mg, 62% yield).

[2-Phenoxy-5-methyl-N-[benzyl(2-pyridyl)methyl]anilido]hafnium(IV)dibenzyl((11)HfBz₂): A diethyl ether solution of 11 (120 mg, 0.565 mmol) wasslowly added to a diethyl ether solution of HfBz₄ (300 mg, 0.551 mmol)forming a brown/orange solution. After stirring for 3 hr, the solventwas removed to give a yellow solid (350 mg, 70%).

[2-Phenoxy-3-tert-butyl-5-methyl-N-[benzyl(2-pyridyl)methyl]anilido]hafnium-(IV)dibenzyl((12)HfBz₂): A THF solution of 12 (125 mg, 0.347 mmol) was slowly addedto a diethyl ether solution of HfBz₄ (189 mg, 0.347 mmol) forming abrown/orange solution. After stirring for 3 hr, the solvent was removedto give a yellow solid (240 mg, 74%).

[2-Phenoxy-3-tert-butyl-5-methyl-N-[phenyl(2-pyridyl)methyl]anilido]hafnium-(IV)dibenzyl((C1)HfBz₂): A THF solution of C1 (96 mg, 0.277 mmol) was slowly addedto a diethyl ether solution of HfBz₄ (155 mg, 0.285 mmol) forming abrown/orange solution. After stirring for 3 hr, the solvent was removedto give a yellow solid (170 mg, 87%).

2-Hydroxybiphenyl-3-carbaldehyde (14): Triethylamine (20.2 g, 27.8 mL,0.20 mol, 2.0 equiv) was added to a solution of 2-phenylphenol (13)(17.0 g, 0.10 mol, 1.0 equiv) in THF (200 mL) followed by solidmagnesium chloride (14.3 g, 0.15 mol, 1.5 equiv). The reactiontemperature increased from 23 to 40° C. over ˜10 min. The reactionmixture was stirred an additional 10 min during which time a light tansuspension formed. Paraformaldehyde (15.0 g, 0.5 mol, 5.0 equiv) wasadded and the mixture heated to reflux with formation of a yellowsuspension. The mixture was refluxed for 2.5 hr, allowed to slowly coolto room temperature and stirred overnight. The mixture was diluted withEtOAc and 1N HCl (300 mL) with mild cooling to keep the reactiontemperature at <25° C. The mixture was transferred to a separatoryfunnel and shaken with an additional 1N HCl (200 mL). The organic phasewas washed with brine (300 mL), dried over Na₂SO₄, filtered and thesolution concentrated under reduced pressure giving a yellow oil thatpartially crystallized. The oily crystalline material was pumped on highvacuum for 1 hr to give 20.6 g (104%) of crude 14 that was used withoutfurther purification.

2-(Benzyloxy)biphenyl-3-carbaldehyde (15): Solid K₂CO₃ (16.3 g, 0.12mol, 1.2 equiv) was added to a solution of crude 14 (20.6 g, ˜0.10 mol,1.0 equiv) in DMF (200 mL) followed by benzyl bromide (17.1 g, 11.9 mL,0.10 mol, 1.0 equiv). The yellow suspension was heated at to 80° C.-90°C. for 4.5 hr. The mixture was cooled to room temperature and stirredfor 48 hr. The mixture was poured into H₂O (750 mL) and the aqueousmixture extracted with EtOAc (500 mL). The organic phase was dilutedwith heptanes (500 mL) and the solution washed with H₂O (3×250 mL),brine (300 mL), dried over Na₂SO₄, filtered and the solutionconcentrated under reduced pressure giving brown oil that crystallized.The crude product was absorbed onto silica gel using dichloromethane anddry-loaded on a column of silica gel (250 g) packed in heptanes. Thecolumn was eluted with heptanes (1 L), 2.5% EtOAc/heptanes (2 L) and 5%EtOAc/heptanes (2 L). Product-containing fractions were concentratedunder reduced pressure. The slightly oily solid was pumped on highvacuum for 0.5 hr, then triturated with cold heptanes (100 mL),filtered, washed with a small volume of heptanes and dried to give 17.8g (62%) of 15 as a white solid.

N-((2-(Benzyloxy)biphenyl-3-yl)methylene)-2-methoxyaniline (17): Asolution of 15 (1.44 g, 5 mmol, 1.0 equiv) and o-anisidine (16) (0.62 g,0.56 mL, 5 mmol, 1.0 equiv) in toluene (15 mL) was refluxed overnightwith H₂O removal (Dean-Stark trap). The mixture was cooled to roomtemperature and concentrated under reduced pressure to give crude 5 as ayellow oil that was used without purification.

N-(1-(2-(Benzyloxy)biphenyl-3-yl)ethyl)-2-methoxyaniline (19): Asolution of crude 17 (˜5 mmol, 1.0 equiv) in THF (25 mL) was cooled inan ice-bath and 3M MeMgBr in Et₂O (4.0 mL, 12.0 mmol, 2.4 equiv) wasadded dropwise via syringe and <5° C. The mixture was stirred at <5° C.for 10 min then allowed to warm to room temperature and stirred 1 hr.The mixture was recooled to ˜8° C. and quenched with saturated NH₄Clsolution (5 mL). The mixture was diluted with H₂O (20 mL) and extractedwith 1:1 EtOAc/heptanes (100 mL). The organic phase was washed withbrine (25 mL), dried over Na₂SO₄, filtered and the solution concentratedunder reduced pressure giving a yellow oil. The crude product wasdissolved in few mL of dichloromethane/heptanes, absorbed onto silicagel and dry-loaded on a column of silica gel (30 g) packed in heptanes.The column was eluted with heptanes (150 mL), 2% EtOAc/heptanes (250 mL)and 3% EtOAc/heptanes (250 mL). Product fractions were concentratedunder reduced pressure to give 1.90 g (93%) of 7 as a nearly colorlessoil.

3-(1-(2-Methoxyphenylamino)ethyl)biphenyl-2-ol (D1): A mixture of 19(1.9 g, 4.6 mmol), 20% Pd—C (˜55% H₂O) and EtOH (50 mL) was hydrogenatedat 20 psi H₂ for 2 hr at which time LCMS show no 19 remained. Themixture was filtered through Celite, washing the Celite pad with EtOH(100 mL). The filtrate was concentrated under reduced pressure to give ayellow-green oil. The crude product was purified on an Analogic MPLC,eluting with a gradient of 0%-20% EtOAc/hexanes to give 0.9 g (60%) ofD1 as a faintly yellow viscous oil. On lengthy standing (>2 months) D1slowly crystallized as a white solid (mp 116.0-116.8° C.).

N-((2-(Benzyloxy)biphenyl-3-yl)(phenyl)methyl-2-methoxyaniline (18): Asolution of 17 (-6 mmol, 1.0 equiv) in THF (30 mL) was cooled to ˜2° C.and 1.8M phenyllithium in di-n-butylether (5 mL, 9 mmol, 1.5 equiv) wasadded dropwise via syringe at <5°. The dark brown solution was stirredat <5° for 0.25 hr then allowed to warm to room temperature and stirred2.5 hr. The mixture was re-cooled to ˜7° C. and quenched with saturatedNH₄Cl solution (10 mL). The mixture was partitioned between 1:1EtOAc/heptanes (150 mL) and H₂O (20 mL). The organic phase was driedover Na₂SO₄, filtered and the solution concentrated under reducedpressure to give a brown oil. The crude product was absorbed onto silicagel and dry-loaded on a column of silica gel (50 g) packed in hexanes.The column was eluted with hexanes (500 mL), 1% MTBE/hexanes (1000 mL).The cleanest product fractions were concentrated under reduced pressureand the residue dried under high vacuum for 1 hr to give 2.0 g (71%) of18 as a white amorphous foam.

Attempted reduction of 18 to3-((2-methoxyphenylamino)(phenyl)methyl)biphenyl-2-ol (D2): A mixture of18 (2.0 g), 4.2 mmol), 20% Pd—C (˜55% H₂O) (0.2 g) and 1:1 EtOAc/EtOH(50 mL) was hydrogenated at 15 psi H₂ for 1.75 hr. TLC (5%MTBE/heptanes) showed 3 components, the lowest R_(f) component beingo-anisidine. The mixture was filtered through Celite, washing the Celitepad with 1:1 EtOAc/EtOH (100 mL). The filtrate was concentrated underreduced pressure to give a light brown oil. The crude product wasabsorbed onto silica gel using DCM and dry-loaded onto a column ofsilica gel (20 g) packed in hexanes. The column was eluted with hexanes(300 mL), 1% MTBE/hexanes (500 mL) and 2% MTBE/hexanes (500 mL). The 2highest R_(f) components eluted together with 1% MTBE/hexanes.Separation of the 2 components was achieved by 2 purifications on aAnalogic MPLC (24 g column, 0%-2% MTBE/hexanes over 20 min and 30 minrespectively) to give 0.12 g of the higher R_(f) component and 0.60 g ofthe lower R_(f) component. Based on ¹H NMR spectroscopy, the structureof the 2 components were as shown below. No D2 was obtained, indicatingthat reductively cleavage of the benzhydryl nitrogen bond in 18 occursmuch more rapidly than reduction of the benzylic ether bond.

2-(Benzyloxy)-3-tert-butylbenzaldehyde (21): A suspension of3-tert-butyl-2-hydroxybenzaldehyde (11.3 g, 63.5 mmol, 1.0 equiv),benzyl bromide (10.8 g, 7.5 mL, 63.5 mmol, 1.0 equiv), powdered K₂CO₃(17.5 g, 127 mmol, 2.0 equiv) and MeCN (300 mL) was refluxed for 4 hr.The pale green suspension was cooled to room temperature, filtered,washing the solids with EtOAc (150 mL). The filtrate was concentratedunder reduced pressure to give a pale green oil. The crude product waschromatographed on silica gel (175 g) packed in heptanes (loaded as asolution in heptanes). The column was eluted with heptanes (1 L), 2%MTBE/heptanes (1 L) and 3% MTBE/heptanes (1.5 L). Product fractions wereconcentrated under reduced pressure to give 14.6 g (86%) of 21 as ayellow oil.

N-(1-(2-(Benzyloxy)-3-tert-butylphenyl)ethyl)2-methoxyaniline (23): Amixture of 21 (1.88 g, 7 mmol, 1.0 equiv), o-anisidine (0.86 g, 0.79 mL,7 mmol, 1.0 equiv), toluene (35 mL) and a crystal of p-toluenesulfonicacid was refluxed for 4 hr with H₂O removal (Dean-Stark trap). Themixture was cooled to room temperature and concentrated under reducedpressure to give crude imine 22 as a yellow-brown oil. Crude 22 wasdissolved in THF (25 mL) and the solution cooled to ˜2° C. 3M MeMgBr inTHF (5 mL, 15 mmol, 2.15 equiv) was added dropwise via syringe. A greencolor developed followed by a yellow-brown color. The reaction mixturewas allowed to warm to room temperature and stirred overnight. Themixture was cooled to ˜10° C., quenched by the slow, dropwise additionof saturated NH₄Cl solution (10 mL) then partitioned between EtOAc (100mL) and H₂O (20 mL). The organic phase was washed with brine (2×40 mL),dried over Na₂SO₄, filtered and the solution concentrated under reducedpressure to give a brown oil. The crude product was absorbed onto silicagel using dichloromethane and dry-loaded onto a column of silica gel (30g) packed in heptanes. The column was eluted with heptanes (100 mL), 2%EtOAc/heptanes (200 mL) and 3% EtOAc/heptanes (200 mL). Productfractions were concentrated under reduced pressure to give 2.3 g (85%)23 as a yellow oil.

2-tert-Butyl-6-(1-2-methoxyphenylamino)ethyl)phenol (D3): A mixture of23 (2.3 g, 5.9 mmol), 20% Pd—C (˜55% H₂O) (0.2 g) and EtOH (50 mL) washydrogenated at ˜20 psi H₂ for 2 hr. The mixture was filtered throughCelite, washing the Celite pad with EtOH (50 mL). The filtrate wasconcentrated under reduced pressure to give a slightly oily tan solid.The crude product was recrystallized from EtOH (˜15 mL) to give 1.02 g(58%) of D3 as a white solid (mp 108.6-109.0° C.).

3-tert-Butyl-2-(4-methoxybenzyloxy)benzaldehyde (24): A suspension of3-tert-butyl-2-hydroxybenzaldehyde (5.0 g, 28.1 mmol, 1.0 equiv),4-methoxybenzyl chloride (4.4 g, 3.8 mL, 28.1 mmol, 1.0 equiv), powderedK₂CO₃ (7.8 g, 56.2 mmol, 2.0 equiv) and MeCN (100 mL) was refluxed for 6hr. The yellow-green suspension was cooled to room temperature andallowed the stand for 48 hr. The suspension was diluted with EtOAc (50mL) and filtered, washing the solids with EtOAc (50 mL). The filtratewas concentrated under reduced pressure to give brown oil. The oil wasdissolved in EtOAc (150 mL) and the solution washed with H₂O (125 mL)and brine (100 mL). The organic phase was dried over Na₂SO₄, filteredand the solution concentrated under reduced pressure to give a brownoil. The crude product was absorbed onto silica gel usingdichloromethane and dry-loaded onto a column of silica gel (100 g)packed in heptanes. The column was eluted with heptanes (500 mL)followed by 2.5% EtOAc/heptanes (1000 mL). Product fractions wereconcentrated under reduced pressure to give a yellow oil. Seeding (seedsobtained by lengthy scratching with cold hexanes) of the oil inducedcrystallization. After crystallization was complete the yellow solid waspumped under high vacuum for 0.5 hr to give 7.5 g (89%) of 24.

N-((3-tert-butyl-2-(4-methoxybenzyloxy)phenyl)(phenyl)methyl)-2-methoxyaniline(26): A mixture of 24 (3.0 g, 10 mmol, 1.0 equiv), o-anisidine (1.3 g,1.2 mL, 100 mmol, 1.0 equiv), toluene (45 mL) containing a crystal ofp-toluenesulfonic was refluxed for 5.5 hr with H₂O removal (Dean-Starktrap). The mixture was cooled to room temperature and stirred overnight.The mixture was concentrated under reduced pressure to give crude imine25 as a yellow-brown oil. Crude 25 was dissolved in THF (75 mL) and thesolution cooled to −2° C. 1.8M phenyllithium in di-n-butylether (15 mL,27 mmol, 2.7 equiv) was added dropwise via syringe at −2° C. to 0° C.The yellow-brown solution was allowed to warm to room temperature andstirred 1.5 hr. The mixture was cooled to ˜10° C., quenched by the slow,dropwise addition of saturated NH₄Cl solution (20 mL) then partitionedbetween 1:1 EtOAc heptanes (150 mL) and H₂O (25 mL). The organic phasewas washed with brine (50 mL), dried over Na₂SO₄, filtered and thesolution concentrated under reduced pressure to give a yellow oil. Thecrude product was absorbed onto silica gel using dichloromethane anddry-loaded onto a column of silica gel (100 g) packed in hexanes. Thecolumn was eluted with hexanes (500 mL), 1% MTME/hexanes (1000 mL) and2% MTBE/hexanes (1500 mL). Product fractions were concentrated underreduced pressure to give a yellowish-white solid that was pumped underhigh vacuum overnight to give 3.6 g (75%) of 26.

Benzyl 2-(benzyloxybiphenyl-3-carboxylate (28): Solid K₂CO₃ (20.7 g, 150mmol, 3.0 equiv) was added to a solution of 3-phenylsalicylic acid (27)(10.7 g, 50 mmol, 1.0 equiv) in DMF (150 mL). Benzyl bromide (18.8 g,13.0 mL, 110 mmol, 2.2 equiv) was added slowly. The reaction temperatureincreased from 25° C. to 28° C. over 0.25 hr. The reaction suspensionheated at ˜80° C. for 5 hr, allowed to cool to room temperature andstand overnight. The mixture was poured into H₂O (750 mL) and extractedwith 5:2 heptanes/MTBE (700 mL). The organic phase was washed with H₂O(3×500 mL), brine (300 mL), dried over Na₂SO₄, filtered and the solutionconcentrated under reduced pressure giving 20.5 g (104%) of crude 28 asa yellow oil that was used without further purification.

2-(Benzyloxybiphenyl-3-carboxylic acid (29): Solid 85% KOH (5.3 g, 80mmol, 1.6 equiv) was added to a solution of crude 28 (20.5 g, ˜50 mmol,1.0 equiv) in EtOH (250 mL) and the mixture refluxed for 16 hr. LCMSshowed some saponification had occurred but the major product was theethyl ester from transesterification. The mixture was cooled to ˜50° C.,KOH (2.7 g, 40 mmol) and H₂O (25 mL) added. The mixture was refluxed foran additional 48 hr. The mixture was cooled to room temperature andconcentrated under reduced pressure to an oily solid. H₂O (200 mL) wasadded, the mixture stirred until all solids had dissolved then extractedwith MTBE (100 mL) followed by 1:1 MTBE/heptanes (100 mL). The aqueousphase was acidified to pH 1 with conc HCl to give a white solid. Theaqueous suspension was extracted with EtOAc (1×250 mL, 1×150 mL). Theorganic phase was washed with brine, dried over Na₂SO₄, filtered and thesolution concentrated under reduced pressure to near dryness. The solidwas triturate with heptanes, filtered and dried to give 8.5 g (56% for 2steps from 27) of 29 as an off-white solid.

tert-Butyl 2-(benzyloxy)biphenyl-3-yl carbamate (30): A mixture of 29(8.5 g, 28 mmol, 1.0 equiv) and toluene (300 mL) was azeotropicallydried (Dean-Stark trap) for 1 hr. The mixture was cooled to ˜40° C. andEt₃N (7.1 g, 9.7 mL, 70 mmol, 2.5 equiv) and tert-butanol (4.6 g, 61.6mmol, 2.2 equiv) were added. The mixture was heated to ˜70° C. anddiphenylphosphoryl azide (8.5 g, 6.6 mL, 1.2 equiv) was added dropwisewhile continuing to heat the mixture. At the end of the addition, thereaction temperature was ˜85° C. and N₂ was being evolved. The mixturewas heated to reflux and held for 5 hr. The mixture was cooled to roomtemperature and washed with H₂O (2×200 mL). The aqueous washings wereback extracted with toluene (100 mL). The combined toluene solution waswashed with brine (200 mL), dried over Na₂SO₄, filtered and the solutionconcentrated under reduced pressure to give a brown oil. The crudeproduct was absorbed onto silica gel using dichloromethane anddry-loaded on a column of silica gel (100 g) packed in heptanes. Thecolumn was eluted with heptanes (700 mL), 1% MTBE/heptanes (1000 mL) and2% MTBE/heptanes (1000 mL). Product fractions were concentrated underreduced pressure to give 6.4 g (61%) of 30 as a nearly colorless oil.

2-(Benzyloxy)biphenyl-3-amine (31): 4M Hydrogen chloride in dioxane (20mL, 80 mmol, 4.7 equiv) was added to a solution of 30 (6.4 g, 17 mmol,1.0 equiv) in EtOAc (200 mL) and the mixture stirred at room temperatureovernight. TLC (10% MTBE/heptanes) showed the reaction was incomplete.The suspension was refluxed for 3.5 hr, cooled to room temperature andstirred overnight. LCMS showed cleavage of the Boc group was incomplete.4M Hydrogen chloride in dioxane (40 mL, 160 mmol, 9.4 equiv) was added,the mixture refluxed for 6.5 hr, cooled to room temperature and stirredovernight. Although TLC showed some 30 remained, the mixture wasconcentrated under reduced pressure to an oily solid. The oily solid wassuspended in H₂O (100 mL) and made alkaline by the slow addition ofsaturated NaHCO₃ solution (100 mL). The aqueous mixture was extractedwith EtOAc (100 mL). The organic solution was washed with brine (100mL), dried over Na₂SO₄, filtered and the solution concentrated underreduced pressure to give a yellow-brown oil. The crude product wasabsorbed onto silica gel using dichloromethane and dry-loaded on acolumn of silica gel (50 g) packed in heptanes. The column was elutedwith heptanes (300 mL), 2% EtOAc/heptanes (500 mL) and 4% EtOAc/heptanes(1000 mL). Product fractions were concentrated under reduced pressure togive 3.5 g (74%) of 31 as a yellow oil after pumping on high vacuum for2.5 hr.

(2-(Benzyloxy)-N-(1-(2-methoxyphenyl))ethyl)biphenyl-3-amine (34): Amixture of 31 (0.70 g, 2.5 mmol, 1.0 equiv), 2-methoxybenzaldehyde (32)(0.35g, 0.3 mL, 2.5 mmol, 1.0 equiv) and toluene (25 mL) containing acrystal of p-toluenesulfonic acid was refluxed for 1.5 hr with H₂Oremoval (Dean-Stark trap). The mixture was cooled to room temperatureand concentrated under reduced pressure to give crude imine 33 as ayellow-brown oil. Crude 33 was dissolved in THF (20 mL) and the solutioncooled to ˜2° C. 3M MeMgBr in Et₂O (1.7 mL, 5 mmol, 2.0 equiv) was addeddropwise via syringe at <5° C. The mixture was allowed to warm to roomtemperature and stirred overnight. The mixture was cooled in an ice bathand quenched with saturated NH₄Cl solution (5 mL). The mixture wasdiluted with H₂O (10 mL) and extracted with 1:1 EtOAc/heptanes (100 mL).The organic phase was washed with brine (2×50 mL), dried over Na₂SO₄,filtered and the solution concentrated under reduced pressure giving ayellow oil. The crude product was absorbed onto silica gel usingdichloromethane and dry-loaded on a column of silica gel packed inheptanes. The column was eluted with heptanes (200 mL), 2% MTBE/heptanes(400 mL). Product fractions were concentrated under reduced pressure andthe residue dried under high vacuum for 1 hr to give 0.41 g (39%) of 34as a pale yellow gummy oil.

3-(1-(2-Methoxyphenyl)ethylamino)biphenyl-2-ol (E1): A mixture of 34(0.41 g, 1.0 mmol), 20% Pd—C (˜55% H₂O) (0.05 g) and EtOH (25 mL) washydrogenated at 20 psi H₂ for 2 hr at which time LCMS show no 33remained. The mixture was filtered through Celite, washing the Celitepad with EtOH. The filtrate was concentrated under reduced pressure togive a dark red-brown oil. TLC (20% EtOAc/heptanes) of the crude productshowed 3 components. LCMS showed E1 along with substantial amounts of2-amino-6-phenylphenol. The crude product was absorbed onto silica gelusing dichloromethane and dry-loaded on a column of silica gel (10 g)packed in hexanes. The column was eluted with hexanes (100 mL), 5%MTBE/hexanes (200 mL). Product fractions were concentrated under reducedpressure and the residue dried under high vacuum for 1 hr to give 0.15 g(48%) of E1 as a pale yellow-green oil. On standing E1 darkened alongwith a concurrent decrease in purity by HPLC. After several weeks E1 haddecomposed into a dark brown gum even though the sample was stored underN₂.

Polymerization Process

Metal-Ligand Solution Procedures

To a 2 mL glass vial, 25 μmol of ligand was added with a spinbar andsealed. Toluene solvent was added to the reaction vial, typicallybetween 0.30-0.70 mL, and stirred for 30-60 minutes at room temperature.An equimolar amount of transition metal precursor was then added to thereaction vial via syringe to form the metal-ligand solution: Method A)0.50 mL of 0.05 mol/L tetrabenzylzirconium or tetrabenzylhafnium(obtained from Strem Chemical, used as received) was added and theresulting metal-ligand solution was stirred at temperatures between 20°C.-100° C. for predetermined reaction times, typically between 10-15 hr,after which the vessel was cooled to room temperature and an additional0.50 mL toluene was added to the reaction vial. Method B) Metalprecursor was added, 0.50 mL of 0.05 mol/Ltetrakis(dimethylamino)zirconium or tetrakis(dimethylamino)hafnium(obtained from Strem Chemical, used as received), and the metal-ligandsolution was stirred at temperatures between 20° C.-100° C. forpredetermined reaction times, typically between 10-15 hr. The glass vialwas cooled to room temperature and 0.50 mL of an 0.50 mol/L solution oftrialkylaluminum, typically triethylaluminum (TEA1) ortri-i-butylaluminum (TiBAl), was added to the metal-ligand solution andstirred for typically 0.5-1.5 hr. Subsequently an aliquot of themetal-ligand solution was removed, typically between 0.10-0.15 mL, anddiluted to final volume of 3.50 mL to afford a final metal-ligandsolution, typically between 0.30-1.00 mmol/L. A small aliquot of theresulting metal-ligand solution was injected into the PPR reactor,typically between 0.025-0.100 μmol, and reaction progress monitored asdescribed below.

Ethylene/1-octene copolymerizations were carried out in a parallelpressure reactor, which is described in U.S. Pat. Nos. 6,306,658,6,455,316, and 6,489,168, WO 00/09255, and Murphy et al., J. Am. Chem.Soc., 2003, 125, 4306-4317, each of which is incorporated herein byreference. A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor, whichcontains 48 individual reaction vessels. The reactor was then closed andeach vessel was individually heated to a set temperature (usuallybetween 50° C. and 100° C.) and pressurized to a pre-determined pressureof ethylene (generally between 75 and 350 psi). 100 μL of 1-octene (637umol) was injected into each reaction vessel through a valve, followedby 500 μL of hexane. A solution of tri-n-octylaluminum was then added toact as a co-catalyst/scavenger, typically 100 μl of 10 mmol/L in hexane(1.0 μmol). The contents of the vessel were then stirred at 800 rpm. Anactivator solution (usually N,N′-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene, 0.40 mmol/L, ˜1.1 equiv)was then injected into the reaction vessel along with 500 μL hexane. Atoluene solution of catalyst was injected (0.020-0.120 μmol) or analiquot of catalyst premix solution (0.020-0.120 μmol), followed by analiquot of hexane (500 μL). All runs were performed in duplicate. Thereaction was then allowed to proceed until a set time limit (usually 30min) or until a set amount of ethylene had been taken up by the reaction(ethylene pressure was maintained in each reaction vessel at the pre-setlevel by computer control). At this point, the reaction was quenched byexposure to air. After the polymerization reaction, the glass vialinsert containing the polymer product and solvent was removed from thepressure cell and the inert atmosphere glovebox and the volatilecomponents were removed using a Genevac HT-12 centrifuge and GenevacVC3000D vacuum evaporator operating at elevated temperature and reducedpressure. The vial was then weighed to determine the yield of thepolymer product. The resultant polymer was analyzed by Rapid GPC (seebelow) to determine the molecular weight, by FT-IR (see below) todetermine comonomer incorporation, and by DSC (see below) to determinemelting point.

For discreet metal complexes (11)HfBz₂, (12)HfBz₂ and (C1)HfBz₂ thefollowing changes to the screening protocol were made: each vessel wasindividually heated to a set temperature (usually 50° C. and 80° C.) andpressurized to a pre-determined pressure of ethylene (generally between75 and 350 psi). 100 uL of 1-octene (637 umol) was injected into eachreaction vessel through a valve, followed by 500 uL of hexane. 100 uL oftri-n-octylaluminum solution (10 mmol/L in hexane, 1 umol) was thenadded to act as a co-catalyst/scavenger. The contents of the vessel werethen stirred at 800 rpm. An activator solution (usuallyN,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene,0.40 mmol/L, ˜1 equiv) was then injected into the reaction vessel alongwith 500 uL hexane, followed by a toluene solution of catalyst (0.40mmol/L, 20-120 nmol) and another aliquot of hexane (500 uL). In atypical run, reaction conditions were varied such that two temperatures,three pressures and four catalyst concentrations were investigated. Allruns were performed in duplicate.

High temperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816,6,491,823, 6,475,391, 6,461,515, 6,436,292, 6,406,632, 6,175,409,6,454,947, 6,260,407, and 6,294,388 each of which is incorporated hereinby reference. This apparatus has a series of three 30 cm×7.5 mm linearcolumns, each containing PLgel 10 um, Mix B. The GPC system wascalibrated using polystyrene standards ranging from 580-3,390,000 g/mol.The system was operated at an eluent flow rate of 2.0 mL/min and an oventemperature of 165° C. 1,2,4-trichlorobenzene was used as the eluent.The polymer samples were dissolved in 1,2,4-trichlorobenzene at aconcentration of 0.1-0.9 mg/mL. 250 uL of a polymer solution wereinjected into the system. The concentration of the polymer in the eluentwas monitored using an evaporative light scattering detector. Themolecular weights obtained are relative to linear polystyrene standards.

Differential Scanning Calorimetry (DSC) measurements were performed on aTA-Q100 instrument to determine the melting point of the polymers.Samples were pre-annealed at 220° C. for 15 minutes and then allowed tocool to room temperature overnight. The samples were then heated to 220°C. at a rate of 100° C./min and then cooled at a rate of 50° C./min.Melting points were collected during the heating period.

The ratio of 1-octene to ethylene incorporated in the polymers (weight%) was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+ IRin reflection mode. Samples were prepared in a thin film format byevaporative deposition techniques. Weight % 1-octene was obtained fromthe ratio of peak heights at 1378 and 4322 cm⁻¹. This method wascalibrated using a set of ethylene/1-octene copolymers with a range ofknown wt % 1-octene content.

Polymerization data shown in Table 1 and 2 is intended to berepresentative of the catalytic behavior of compounds of the inventionand not comprehensive.

TABLE 1 Selected High Throughput Polymerization Results for the DiscreteMetal Complexes (11)HfBz₂, (12)HfBz₂ and (C1)HfBz₂ Activity Amount TempPressure Time Yield (g/mmol Mw MWD Tm Example Catalyst (nmol) (° C.)(psi) (sec) (mg) h bar) (kDa) (Mw/Mn) (° C.) 1 (11)HfBz₂ 40 80 350 18005 11 ND ND ND 2 (11)HfBz₂ 80 50 350 1800 6 6 ND ND ND 3 (11)HfBz₂ 80 50350 1800 6 6 ND ND ND 4 (11)HfBz₂ 80 80 200 1800 8 15 ND ND ND 5(11)HfBz₂ 80 80 200 1800 9 15 ND ND ND 6 (11)HfBz₂ 80 80 350 1800 10 11174 1.5 130 7 (11)HfBz₂ 80 80 350 1800 12 12 177 1.5 131 8 (11)HfBz₂ 12050 200 1800 7 8 ND ND ND 9 (11)HfBz₂ 120 80 200 1800 14 16 178 1.6 12710 (11)HfBz₂ 120 80 200 1800 15 17 180 1.5 128 11 (11)HfBz₂ 120 80 3501800 14 9 179 1.6 131 12 (11)HfBz₂ 120 80 350 1800 12 8 182 1.6 131 13(12)HfBz₂ 120 80 200 1800 7 4 ND ND ND 14 (12)HfBz₂ 120 80 200 1800 6 7ND ND ND 15 (12)HfBz₂ 120 80 350 1800 7 3 ND ND ND 16 (12)HfBz₂ 120 80350 1800 6 3 ND ND ND 17 (C1)HfBz₂ 80 80 350 1800 8 14 ND ND ND 18(C1)HfBz₂ 80 80 350 1800 8 14 ND ND ND 19 (C1)HfBz₂ 80 80 350 1800 13 13152 1.3 130 20 (C1)HfBz₂ 80 80 350 1800 13 13 156 1.3 131 21 (C1)HfBz₂120 80 350 1800 16 18 155 1.3 128 22 (C1)HfBz₂ 120 80 350 1800 15 16 1611.3 128 23 (C1)HfBz₂ 120 80 350 1800 18 12 158 1.3 131 24 (C1)HfBz₂ 12080 350 1800 18 12 161 1.3 130

TABLE 2 Selected High Throughput Polymerization Results for In SituComplexations Ligand Metal Activity amount Metal amount Temp PressureTime Yield (g/mmol Mw MWD Comonomer Example Ligand (nmol) Source (nmol)(° C.) (psi) (sec) (mg) h bar) (kDa) (Mw/Mn) (wt %) 25 A1 163 Zr(NR2)481 80 75 1639 31 161 768 20.0 26 A1 100 Zr(NR2)4 98 80 75 1801 27 1051261 8.8 27 A3 80 ZrBz4 78 80 75 1800 5 26 ND ND 28 A3 163 Zr(NR2)4 8180 75 1800 25 118 3158 90.6 29 A3 60 Zr(NR2)4 60 80 75 1800 20 130 78310.5 30 A4 80 ZrBz4 78 80 75 1802 5 26 151 1.9 31 A4 163 Zr(NR2)4 81 8075 1802 21 100 953 38.9 32 B1 80 ZrBz4 78 80 75 1800 8 39 1653 2.0 33 B182 Zr(NR2)4 81 80 75 1399 35 214 818 22.0 34 B1 163 Zr(NR2)4 81 80 75935 30 278 597 22.2 35 B1 100 Zr(NR2)4 98 80 75 1801 37 144 817 15.9 36B2 80 ZrBz4 78 80 75 1801 17 82 663 6.6 4.45 37 B2 60 Zr(NR2)4 60 80 751802 18 116 613 9.4 38 B2 163 Zr(NR2)4 80 80 75 1801 17 83 821 30.5 39B2 99 Zr(NR2)4 98 80 75 1802 13 51 1034 21.6 40 B3 80 ZrBz4 78 80 751802 8 40 386 2.6 41 B3 60 Zr(NR2)4 60 80 75 1801 6 38 212 2.1 42 B3 163Zr(NR2)4 81 80 75 1802 27 128 670 27.4 43 B3 99 Zr(NR2)4 98 80 75 180110 39 637 17.9 44 D1 80 ZrBz4 78 80 75 1802 9 43 195 1.7 45 D3 80 ZrBz478 80 75 1800 7 33 190 1.5

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.

What is claimed is:
 1. A transition metal catalyst compound representedby one of the structures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is0, 1, 2 or 3; each R¹ and R² , R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹³, and R¹²is, independently, a hydrogen, a hydrocarbyl, a substitutedhydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, analkoxide, a sulfide, an amide, a phosphide, a silyl or an anionicheteroatom-containing group, or independently, may join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure; L is a neutral ligandbonded to M; M is Hf, Zr or Ti; m is 0, 1 or 2 and indicates the absenceor presence of L; and n is 1 or
 2. 2. The compound according to claim 1,wherein the structure is C.
 3. The compound of claim 1, wherein n is 1and w is 2 or
 3. 4. The compound of claim 1, wherein R⁷ is methyl, ethyln-butyl, t-butyl, benzyl, phenyl 2-methylphenyl, 1-naphthalene,9-phenanthroline, 2-trifluoromethylphenyl, or mesyl.
 5. The compoundaccording to claim 1, wherein n is 1 and the structure is:

wherein w is 2 or
 3. 6. The compound of claim 1, wherein at least one ofR⁷ or R¹³ is not a hydrogen atom.
 7. The compound of claim 1, whereinwhen R¹² is a hydrogen atom for structure A or B, M may react with theR¹² hydrogen atom to generate HX and a bond is formed between the carbonbearing position at R¹² and M.
 8. The compound of claim 1, wherein theneutral ligand L includes molecules of pyridine, acetonitrile, diethylether, tetrahydrofuran, dimethylaniline, trimethylamine, tributylamine,trimethylphosphine, triphenylphosphine, lithium chloride, ethylene,propylene, butene, octene, or styrene.
 9. A transition metal catalystcomposition represented by one of the structures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is0, 1, 2 or 3; each R¹ and R² , R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰,R¹¹,R¹³,and R¹², is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, ahalogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or ananionic heteroatom-containing group, or independently, may join togetherto form a C₄ to C₆₂ cyclic or polycyclic ring structure; L is a neutralligand bonded to M; M is Hf, Zr or Ti; m is 0, 1 or 2 and indicates theabsence or presence of L; n is 1 or 2; and an activator.
 10. Thecomposition according to claim 9, wherein the structure is C.
 11. Thecomposition of claim 9, wherein n is 1 and w is 2 or
 3. 12. Thecomposition of claim 9, wherein R⁷ is methyl, ethyl n-butyl, t-butyl,benzyl, phenyl 2-methylphenyl, 1-naphthalene, 9-phenanthroline,2trifluoromethylphenyl, or mesyl.
 13. The composition according to claim9 , wherein n is 1 and the structure is:

wherein Me is methyl and w is 2 or
 3. 14. The composition of claim 9,wherein the neutral ligand L includes molecules of pyridine,acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, or styrene.
 15. Aprocess for polymerization comprising: contacting ethylene and,optionally, one or more unsaturated monomers with a transition metalcatalyst compound represented by one of the structures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is0, 1, 2 or 3; each R¹ and R² R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹,R¹³,and R¹², is, independently, a hydrogen, a hydrocarbyl, a substitutedhydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, analkoxide, a sulfide, an amide, a phosphide, a silyl or an anionicheteroatom-containing group, or independently, may join together to forma C₄ to C₆₂ cyclic or polycyclic ring structure; L is a neutral ligandbonded to M; M is Hf, Zr or Ti; m is 0, 1 or 2 and indicates the absenceor presence of L; and n is 1 or
 2. 16. The process according to claim15, wherein the structure is C.
 17. The process of claim 15, wherein nis 1 and w is 2 or
 3. 18. The process of claim 15, wherein R⁷ is methyl,ethyl n-butyl, t-butyl, benzyl, phenyl 2-methylphenyl, 1-naphthalene,9-phenanthroline, 2-trifluoromethylphenyl, or mesyl.
 19. The processaccording to claim 11, wherein n is 1 and the structure is:

wherein Me is methyl and w is 2 or
 3. 20. The process of claim 15,wherein the neutral ligand L includes molecules of pyridine,acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, or styrene.
 21. Aprocess for polymerization comprising: contacting ethylene and,optionally, one or more unsaturated monomers with a transition metalcatalyst composition represented by one of the structures:

wherein each X is, independently, a hydride, a halogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is0, 1, 2 or 3; each R¹ and R² , R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹³, and R¹², is, independently, a hydrogen, a hydrocarbyl, asubstituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, ahalogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or ananionic heteroatom-containing group, or independently, may join togetherto form a C₄ to C₆₂ cyclic or polycyclic ring structure; L is a neutralligand bonded to M; M is Hf, Zr or Ti; m is 0, 1 or 2 and indicates theabsence or presence of L; n is 1 or 2; and an activator.
 22. The processaccording to claim 21, wherein the structure is C.
 23. The processaccording to either of claim 21 or 22, wherein n is 1 and w is 2 or 3.24. The process of claim 21, wherein R⁷ is methyl, ethyl n-butyl,t-butyl, benzyl, phenyl 2-methylphenyl, 1-naphthalene, 9-phenanthroline,2-trifluoromethylphenyl, or mesityl.
 25. The process according to claim21, wherein n is 1 and the structure is:

wherein Me is methyl and w is 2 or
 3. 26. The process of claim 21,wherein the neutral ligand L includes molecules of pyridine,acetonitrile, diethyl ether, tetrahydrofuran, dimethylaniline,trimethylamine, tributylamine, trimethylphosphine, triphenylphosphine,lithium chloride, ethylene, propylene, butene, octene, or styrene. 27.The process of claim 21, wherein the product of the polymerizationprocess is homopolyethylene.